{"found":55760,"hits":[{"document":{"authors":[{"contributor_roles":[],"family":"Eden","given":"Terence","url":"https://orcid.org/0000-0002-9265-9069"}],"blog":{"authors":null,"community_id":"61ce553a-bafd-4aba-a952-d3bab5e85bcc","created":1788652800,"current_feed_url":null,"description":"Regular nonsense about tech and its effects \ud83d\ude43","doi":"https://doi.org/10.59350/shkspr","favicon":"https://rogue-scholar.org/api/communities/61ce553a-bafd-4aba-a952-d3bab5e85bcc/logo","feed_format":"application/atom+xml","feed_url":"https://shkspr.mobi/blog/feed/atom/?cat=-1982&HTTP_REFERER=DOI","filter":null,"generator":"WordPress","home_page_url":"https://shkspr.mobi/blog","issn":"2753-1570","language":"eng","license":"https://creativecommons.org/licenses/by/4.0/legalcode","prefix":"10.59350","relative_url":null,"secure":true,"slug":"shkspr","status":"active","subfield":"1712","title":"Terence Eden's Blog","updated":1789040050,"use_api":false},"blog_name":"Terence Eden's Blog","blog_slug":"shkspr","content_html":"

For years, I've had a test-card at the start of my slides. Before I start my talk, I can immediately see if the aspect ratio is wrong, colours are off, or any other visual issues with the presentation.

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A few years ago I was invited to give a talk and was assured that the venue was set up for audio as well as video. I dutifully filled my slides with with demo videos containing sound. None of them worked. Somewhere between the HDMI output of the presentation laptop and the speakers, the audio went AWOL.

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Ever since then, I've placed an audio test slide at the start of my presentations. There's a good range of videos on YouTube - pick one you like, embed it into your slides, and play it before your talk starts.

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Over the years, I've found the following \"bugs\" with event AV setups:

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Whether events are professionally run or community managed, you can never guarantee that sound will work. Add subtitles to your videos. If possible, add a sign-language interpreter. And, if all else fails, hold your microphone to your laptop's speakers.

\n\"\"","doi":"https://doi.org/10.59350/gm6k5-zfd63","guid":"https://shkspr.mobi/blog/?p=68346","image":"https://shkspr.mobi/blog/wp-content/uploads/2017/10/Test-Card-on-a-screen.jpg","language":"en","license":"https://creativecommons.org/licenses/by/4.0/legalcode","published_at":1788998400,"rid":"na75e-q2e41","summary":"For years, I've had a test-card at the start of my slides. Before I start my talk, I can immediately see if the aspect ratio is wrong, colours are off, or any other visual issues with the presentation. A few years ago I was invited to give a talk and was assured that the venue was set up for audio as well as video. I dutifully filled my slides with with demo videos containing sound.","tags":["Presentations"],"title":"Put an AV test at the start of your slides","updated_at":1789119908,"url":"https://shkspr.mobi/blog/2026/09/put-an-av-test-at-the-start-of-your-slides/","version":"v1"}},{"document":{"authors":[{"contributor_roles":[],"name":"Ko-AutorInnen"}],"blog":{"authors":null,"community_id":"ad6b31bb-31f3-4277-bcf1-7bc662d83893","created":1740441600,"current_feed_url":null,"description":"Netzwerk Fluchtforschung ist ein multi-disziplin\u00e4res Netzwerk von Wissenschaftler*innen die zu jeglichen Aspekten von Flucht und Fl\u00fcchtlingsschutz forschen.","doi":"https://doi.org/10.59350/fluchtforschung","favicon":"https://rogue-scholar.org/api/communities/ad6b31bb-31f3-4277-bcf1-7bc662d83893/logo","feed_format":"application/atom+xml","feed_url":"https://fluchtforschung.net/feed/atom/","filter":null,"generator":"WordPress","home_page_url":"https://fluchtforschung.net/","issn":null,"language":"deu","license":"https://creativecommons.org/licenses/by/4.0/legalcode","prefix":"10.59350","relative_url":null,"secure":true,"slug":"fluchtforschung","status":"active","subfield":"3312","title":"Netzwerk Fluchtforschung","updated":1789113368,"use_api":true},"blog_name":"Netzwerk Fluchtforschung","blog_slug":"fluchtforschung","content_html":"

Der Ende Juli verabschiedete Regierungsentwurf des KI-Migrationsverwaltungsgesetzes (KIMVG) will eine breite Rechtsgrundlage f\u00fcr den Einsatz von K\u00fcnstlicher Intelligenz (KI) in Visa-, Aufenthalts- und Asylverfahren schaffen. Der Gesetzesentwurf sieht vor, personenbezogene Daten f\u00fcr die Entwicklung eigener KI-Systeme zu verarbeiten, Antr\u00e4ge automatisiert mit \u00f6ffentlich zug\u00e4nglichen Internetquellen abzugleichen und ein KI-gest\u00fctztes Verfahrensmonitoring einzuf\u00fchren. Die Bundesregierung begr\u00fcndet das Gesetz mit dem Verweis auf knappe Ressourcen und dem Ziel, Effizienz, Qualit\u00e4t und Sicherheit der Verfahren zu verbessern. Gleichzeitig weisen zivilgesellschaftliche Akteur*innen auf rechtliche L\u00fccken, zu weitreichende Befugnisse und eine Vielzahl offener Fragen hin. Dieser Blogpost analysiert die Grundelemente des KIMVG, gibt einen \u00dcberblick \u00fcber die Einsch\u00e4tzungen und Kritik der Zivilgesellschaft und diskutiert die Wichtigkeit einer breiten gesellschaftlichen Beteiligung bei der Diskussion \u00fcber die Regulierung von KI-Systemen in der Migrations- und Asylverwaltung.

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Am 29.07.2026 beschloss das Bundeskabinett den Regierungsentwurf des sogenannten KI-Migrationsverwaltungsgesetzes (KIMVG), der zu einer Weichenstellung f\u00fcr die Zukunft der deutschen Asyl- und Migrationsverwaltung werden k\u00f6nnte. Mit \u00c4nderungen und Erg\u00e4nzungen des Asylgesetzes und des Aufenthaltsgesetzes will der Entwurf eine breite Rechtsgrundlage f\u00fcr den Einsatz von KI in der Migrationsverwaltung schaffen, konkret bei Visa-, Aufenthalts- und Asylverfahren. Dies betrifft insbesondere drei Punkte: Erstens, ein \"automatisiertes Verfahrensmonitoring\", bei dem abgeschlossene Verfahren KI-gest\u00fctzt ausgewertet werden sollen, um Entscheidungsstrukturen zu identifizieren und Potenziale f\u00fcr Standardisierung und Beschleunigung zu erkennen. Zweitens \u2013 bei begr\u00fcndeten Zweifeln \u2013 ein automatisierter Abgleich von Angaben mit Quellen aus dem Internet, zum Beispiel aus sozialen Netzwerken. Drittens, eine Nutzung von personenbezogenen Daten, um beh\u00f6rdliche KI-Systeme zuk\u00fcnftig zu trainieren, zu validieren und zu testen. Das beim Bundesministerium des Inneren (BMI) angesiedelte Gesetzgebungsverfahren geht auf ein Eckpunktepapier des BMI und des Ausw\u00e4rtigen Amts (AA) von 2025 zur\u00fcck. Nach Ver\u00f6ffentlichung des ersten Referentenentwurfs des KIMVG am 25.06.2026 wurden eine Reihe von Verb\u00e4nden und zivilgesellschaftlicher Organisationen um Stellungnahme innerhalb einer Woche gebeten. Die Kurzfristigkeit wurde von allen stellungnehmenden Akteur*innen kritisiert. Der Deutsche Caritasverband e.V. schreibt beispielsweise, dass \"eine vertiefte fachliche und rechtliche Pr\u00fcfung des Entwurfs [angesichts der au\u00dferordentlich kurzen Frist] nicht m\u00f6glich war\". Als n\u00e4chste Schritte im Gesetzgebungsverfahren folgen Abstimmungen im Bundestag und Bundesrat \u2013 eine genaue Timeline ist jedoch zum aktuellen Zeitpunkt ungewiss.

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Was versteht die Bundesregierung als zentrales Problem?

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Bereits das Eckpunktepapier von AA und BMI von 2025 begr\u00fcndet die Notwendigkeit f\u00fcr KI und Automatisierung mit Verweis auf \"gesteigerte Effizienz\" und \"mehr Sicherheit\". Durch (Teil-)Automatisierung sollen Verfahren \"schneller und weniger ressourcenintensiv\" und Wartezeiten verk\u00fcrzt werden, wodurch insbesondere die Fachkr\u00e4fteeinwanderung profitiere. Ebenso verweist der Regierungsentwurf des KIMVG auf \"stetig steigende Antragsaufkommen\", begrenzte personelle und organisatorische Kapazit\u00e4ten, sowie eine uneinheitliche Verwaltungspraxis und Rechtsanwendung. Das Gesetz solle nun einen \"rechtssicheren und datenschutzkonformen Rahmen\" schaffen, um \"durch den Einsatz digitaler Verfahren \u2013 insbesondere K\u00fcnstlicher Intelligenz \u2013 die Effizienz, Einheitlichkeit, Qualit\u00e4t und Sicherheit\" der Verfahren zu erh\u00f6hen.

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Der Regierungsentwurf des KIMVG wird damit durchg\u00e4ngig mit einer bestimmten Problemdiagnose begr\u00fcndet: Komplexe rechtliche Vorgaben, die Vielzahl von Antragsstrecken und Antr\u00e4gen f\u00fchrten zu einer uneinheitlichen Verwaltungspraxis; ohne strukturelle Anpassungen sei angesichts begrenzter Ressourcen eine zus\u00e4tzliche Belastung der Verfahren absehbar. Diese Diagnose trifft ein reales Problem: Der \u00f6ffentliche Dienst in Deutschland und insbesondere die Ausl\u00e4nderbeh\u00f6rden leiden unter Personalmangel, und langwierige Verfahren belasten sowohl Antragsstellende als auch die zust\u00e4ndigen Beamt*innen. Was die Antragszahlen betrifft, ist die Faktenlage jedoch weniger eindeutig. Die Gesamtzahl der Asylantr\u00e4ge beispielsweise sank von 330.000 im Jahr 2023 auf rund 130.000 im Jahr 2025.

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Vor diesem Hintergrund ist es bemerkenswert, dass der Entwurf KI als einzig denkbare und kostenneutrale L\u00f6sung darstellt und dabei zus\u00e4tzliche Ressourcen f\u00fcr die Ausl\u00e4nderbeh\u00f6rden oder vereinfachte Verfahrensregeln als Alternativen ebenso ausblendet wie die Kosten, die mit der Einf\u00fchrung von KI einhergehen werden. Die Forschung warnt vor der Annahme, dass die Einf\u00fchrung von KI in der \u00f6ffentlichen Verwaltung automatisch Kosteneinsparungen und Effizienzgewinne mit sich bringt. Wie auch die Deutsche Vereinigung f\u00fcr Datenschutz (DVD) in ihrer Stellungnahme zum Regierungsentwurf anmerkt, erfordert eine weitergehende Digitalisierung und die Einf\u00fchrung von KI in der deutschen Migrationsverwaltung zun\u00e4chst zus\u00e4tzliches Personal, Schulungen und technische Infrastruktur \u2013 Kosten, die der Entwurf nicht ber\u00fccksichtigt. Die Argumentation im Entwurf steht f\u00fcr eine allgemeinere Tendenz, ein im Kern politisches Problem \u2013 Personalmangel, Ressourcenverteilung, komplexe verwaltungs- und rechtstechnische Sachverhalte \u2013 vorrangig durch neue Technologie l\u00f6sen zu wollen.

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Was kritisieren Interessengruppen und Zivilgesellschaft?

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Im Rahmen des Gesetzgebungsprozesses ver\u00f6ffentlichte das BMI sechs Stellungnahmen von Bundesvereinigungen, Verb\u00e4nden und B\u00fcrgerrechtsorganisationen: der AWO Bundesverband e.V., die Bundesvereinigung der kommunalen Spitzenverb\u00e4nde, die Deutsche Vereinigung f\u00fcr Datenschutz (DVD) e.V., der Deutsche Caritasverband e.V., Pro Asyl sowie Statefree e.V. Dar\u00fcber hinaus kommentierten weitere Akteur*innen den Gesetzesentwurf auf ihren eigenen Webseiten, wie beispielsweise netzpolitik.org, AlgorithmWatch oder auch die Gesellschaft f\u00fcr Informatik e.V.

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Mehrere Verb\u00e4nde erkennen an, dass die Digitalisierung der Migrationsverwaltung dringend n\u00f6tig ist, um Verfahren zu beschleunigen. Dennoch dominiert in den Stellungnahmen eine eher kritische Haltung, insbesondere mit Blick auf drei Punkte: (1) den fehlenden und unzureichenden Rechtsschutz; (2) Risiken von Diskriminierung und Bias; und (3) die Vagheit des Entwurfs, auch hinsichtlich der Entscheidungsmacht von KI-Systemen.

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Ein erster Kritikpunkt, der sich durch nahezu alle Stellungnahmen der Verb\u00e4nde zieht, betrifft die Vereinbarkeit mit Datenschutz, Verfassungsrecht und EU-Recht. Mehrere Verb\u00e4nde \u00e4u\u00dfern datenschutzrechtliche Bedenken, da die Nutzung personenbezogener Daten insgesamt zu umfassend sei. Der Entwurf erlaubt, unter bestimmten Umst\u00e4nden, auch die Verwendung nicht anonymisierter Daten. Hinsichtlich des Verfahrensmonitorings sollen selbst biometrische Daten weiterverarbeitet werden k\u00f6nnen, wenn ihre Aussonderung \"technisch unm\u00f6glich ist oder unverh\u00e4ltnism\u00e4\u00dfig hohen technischen Aufwand erfordert\". Auch ist fraglich, ob sensible, personenbezogene Daten wieder vollst\u00e4ndig gel\u00f6scht werden k\u00f6nnen, nachdem sie f\u00fcr die Entwicklung von KI-Systemen und insbesondere von Large Language Models (LLMs) genutzt wurden \u2013 Modelle, die basierend auf gro\u00dfen Datenmengen darauf abzielen, menschliche Sprache zu analysieren und zu generieren. Laut Pro Asyl verfehle der Entwurf au\u00dferdem die Anforderungen an gerechte und faire Verwaltungsverfahren im Sinne grundrechtskonformer Verfahrensgestaltung und effektiven Rechtsschutzes und schaffe stattdessen die Grundlage f\u00fcr \"intransparente, algorithmisch gesteuerte Entscheidungsprozesse\". Zwar postuliert der Entwurf, allgemein mit dem EU-Recht konform zu sein, doch werden mehreren Verb\u00e4nden und auch Wissenschaftler*innen zufolge Vorgaben hinsichtlich der EU Datenschutz-Grundverordnung (DSGVO) und der EU KI-Verordnung (KI-VO) missachtet. So beruft sich der Gesetzentwurf beispielsweise auf \u00a7 10 Abs. 3 der KI-VO, wonach Trainingsdaten \"relevant, hinreichend repr\u00e4sentativ, fehlerfrei und vollst\u00e4ndig\" sein m\u00fcssen. Wie die Deutsche Vereinigung f\u00fcr Datenschutz (DVD) in ihrer Stellungnahme betont, ist dies im Migrationskontext eine hohe H\u00fcrde: Das Ausl\u00e4nderzentralregister (AZR), das weitgehend auf denselben Datenquellen basiert, mit denen die KI sehr wahrscheinlich trainiert werden w\u00fcrde, weist bekannterma\u00dfen erhebliche Genauigkeitsdefizite auf, die dadurch versch\u00e4rft werden, dass sich viele der relevanten Merkmale schnell \u00e4ndern und veralten.

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Ein zweiter akteurs\u00fcbergreifender Kritikpunkt betrifft Fragen rund um Diskriminierung und Bias der geplanten KI-Systeme. Der Entwurf nimmt die Beh\u00f6rden in die Pflicht, keine diskriminierenden Algorithmen herauszubilden oder zu verwenden, ohne jedoch zu erl\u00e4utern, wie das sichergestellt werden soll. Konkret besteht hier ein zentrales technisches Problem: Gro\u00dfe Sprachmodelle generieren Outputs durch erlernte Muster und statistische Wahrscheinlichkeiten auf Grundlage von Trainingsdaten. Werden umfassende Daten aus bereits abgeschlossenen Verfahren als Grundlage f\u00fcr ein KI-Training genutzt, k\u00f6nnten bereits existierende Verzerrungen reproduziert werden. So k\u00f6nne die Datengrundlage bei der KI-Entwicklung je nach Auswahl diskriminierende Stereotype widerspiegeln oder festigen, warnt Pro Asyl. Eine wirksame Gegenma\u00dfnahme bestehe, der Deutschen Vereinigung f\u00fcr Datenschutz (DVD) zufolge, beispielsweise in verpflichtenden, externen und unabh\u00e4ngigen Kontrollverfahren.

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Ein dritter Kritikpunkt der Organisationen betrifft die Vagheit und mangelnde Bestimmtheit des Entwurfs, insbesondere mit Blick auf die Frage, wie viel Entscheidungsmacht KI-Systeme in Verfahren perspektivisch h\u00e4tten. Laut Entwurf verbleiben individuelle verfahrenstechnische Entscheidungen weiterhin in menschlicher Verantwortung und das BMI betont im Regierungsentwurf, dass \"die individuelle Pr\u00fcfung vollst\u00e4ndig in der Verantwortung der zust\u00e4ndigen Mitarbeitenden liege\". Hier kritisieren Verb\u00e4nde allerdings, dass unklar bleibt, wie dem sogenannten Automation-Bias vorgebeugt werden soll \u2013 also der Tendenz, maschinellen Entscheidungen eher zu vertrauen als dem menschlichen Urteil. Ohne flankierende Ma\u00dfnahmen k\u00f6nnten Entscheidungen so faktisch KI-basiert erfolgen. Die Stellungnahmen fordern hier mehrfach eine verbindliches Human-in-the-Loop-Prinzip und eine klarere Definition des Verh\u00e4ltnisses zwischen der KI-Nutzung f\u00fcr das allgemeine Verfahrensmonitoring und der Einzelfallentscheidung.

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Unklarheiten bestehen jedoch nicht nur hinsichtlich der Entscheidungsmacht, sondern ziehen sich durch den gesamten Regierungsentwurf. Die Verb\u00e4nde kritisieren, dass weitreichende Rechtsgrundlagen f\u00fcr den KI-Einsatz geschaffen werden, ohne hinreichend festzulegen, welche konkreten Systeme k\u00fcnftig f\u00fcr welche Zwecke eingesetzt werden d\u00fcrfen und wo ihre Grenzen liegen. Der AWO Bundesverband e.V. bem\u00e4ngelt entsprechend, dass von regelbasierter Dokumentenerkennung bis zur vollautomatisierten Risikoeinsch\u00e4tzung nahezu alle Szenarien denkbar seien.

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Angesichts dieser sich durch den Entwurf ziehenden Unklarheiten fordern Verb\u00e4nde teils eine intensive \u00dcberarbeitung, teils ein Zur\u00fcckziehen des Entwurfs.

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Was dar\u00fcber hinaus noch offen bleibt

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\u00dcber die drei zentralen Kritikpunkte der Zivilgesellschaft und Interessengruppen hinaus l\u00e4sst der Entwurf eine lange Liste weiterer Fragen unbeantwortet. Welche Transparenzma\u00dfnahmen w\u00fcrden f\u00fcr Migrantinnen und Asylbewerberinnen gelten, deren F\u00e4lle analysiert werden? Wie w\u00fcrden Sachbearbeiter*innen im Umgang mit diesen Systemen geschult? Wie lie\u00dfe sich verhindern, dass im Zuge einer uneinheitlich fortschreitenden Digitalisierung parallele, inkompatible Systeme zwischen den Beh\u00f6rden entstehen? Wie w\u00fcrden die Systeme der Komplexit\u00e4t unterschiedlicher Verfahrensarten und individueller Umst\u00e4nde gerecht werden?

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Bei vielen der Vorschl\u00e4ge des Entwurfs h\u00e4ngt es au\u00dferdem von der technischen Ausgestaltung und flankierenden Ma\u00dfnahmen, zum Beispiel Schulungen ab, wie rechtskonform und gewinnbringend sie f\u00fcr die Verwaltung aber auch Antragsstellende sein k\u00f6nnen. Das automatisierte Verfahrensmonitoring beispielsweise ist laut Entwurf auf die Gewinnung \"verallgemeinerungsf\u00e4higer Erkenntnisse\" ausgerichtet. Einerseits kann die Analyse vergangener Entscheidungen dazu beitragen, Inkonsistenzen, Diskriminierungsmuster oder strukturelle Fehlentwicklungen in der bisherigen Entscheidungspraxis sichtbar zu machen. Andererseits kann dieselbe Analyse eine normalisierende Wirkung entfalten, indem bestehende Entscheidungsmuster zum Ausgangspunkt f\u00fcr die Weiterentwicklung zuk\u00fcnftiger Verfahren werden. Insbesondere in Asylverfahren, in denen Anerkennungsquoten auch f\u00fcr Personen der gleichen Nationalit\u00e4t, mit \u00e4hnlichen Schutzgesuchen von politischen Faktoren beeinflusst werden und \u00fcber die Zeit variieren k\u00f6nnen, stellt sich die Frage, wie genau \"Muster\" erkannt und aktuelle Entscheidungspraktiken beeinflussen sollen.

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Nat\u00fcrlich l\u00e4sst sich nicht erwarten, dass ein Gesetzentwurf all diese Fragen bereits abschlie\u00dfend beantwortet. Bemerkenswert ist dennoch, wie unbestimmt der Entwurf an zentralen Stellen bleibt. Der Umfang dieser offenen Fragen ist selbst Teil der Kritik, wie auch zivilgesellschaftliche Organisationen und Wissenschaftler*innen anmerken: Ein Gesetz, das eine dauerhafte Rechtsgrundlage f\u00fcr den Einsatz von KI in der Migrationsverwaltung schaffen soll, \u00fcberl\u00e4sst zahlreiche operative Details \u2013 jene Details also, die dar\u00fcber entscheiden w\u00fcrden, ob die Systeme in der Praxis fair, nachvollziehbar und wirksam sind und wie stark KI die tats\u00e4chliche Entscheidungsfindung beeinflusst \u2013 einer sp\u00e4teren Kl\u00e4rung.

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KI in der Migrationsverwaltung weiterdenken

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Neben Kritikpunkten an dem konkreten Gesetzentwurf kristallisieren sich auch einige grunds\u00e4tzliche Fragen sowohl zum Prozess der Gesetzfindung als auch allgemein zum Einsatz von KI in der Migrationsverwaltung heraus. In Zeiten, in denen Digitalisierung bereits ein nicht wegzudenkender Bestandteil in der Gesellschaft scheint, geht es dabei vor allem um die Frage wie diese neue Dimension der Digitalisierung gestaltet werden kann, wer dabei beteiligt werden sollte und was wir aus anderen Kontexten lernen k\u00f6nnen.

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Fragen dieser Tragweite w\u00fcrden eigentlich eine breite gesellschaftspolitische Debatte erfordern. Eine solche Debatte hat bislang jedoch kaum stattgefunden \u2013 die Bundesregierung treibt den Gesetzgebungsprozess stattdessen mit erkennbarem zeitlichem Druck voran, was sich auch in der kurzen Beteiligungsfrist der Verb\u00e4nde widerspiegelt. Der Zeitdruck auf Seiten der Regierung geht bereits aus dem Eckpunktepapier von AA und BMI von 2025 hervor, wenn beispielsweise ein \"schneller, wirksamer und sicherer Modernisierungserfolg\" als erkl\u00e4rtes Ziel formuliert wird. Auch sah das Papier f\u00fcr den Sommer dieses Jahres eigentlich bereits die Verabschiedung des Gesetzes durch den Bundestag vor.

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Dem entgegen steht die Position, wonach eine potenziell so grundlegende Neuausrichtung der Migrationsverwaltung und Entscheidungspraxis durch zentrale Akteur*innen des Politikfeldes vorbereitet und durch den Gesetzgebungsprozess hinweg begleitet werden muss. So fordert der AWO Bundesverband e.V. beispielsweise \"eine sorgf\u00e4ltige rechtliche, ethische und praktische Pr\u00fcfung\", die viele der grunds\u00e4tzlichen Fragen vor einer Einf\u00fchrung von KI-Systemen beleuchten m\u00fcsse. Konkret schl\u00e4gt der Verband deshalb eine unabh\u00e4ngige und interdisziplin\u00e4r besetzte Expert*innenkommission vor, um zun\u00e4chst zu pr\u00fcfen, \"ob und unter welchen Voraussetzungen der Einsatz von KI-Systemen in Verwaltungsverfahren mit den Anforderungen des Rechtsstaats sowie den Rechten der Betroffenen vereinbar ist\". Offen bleibt zudem, welche Akteur*innen die von KI-Systemen Betroffenen angemessen repr\u00e4sentieren k\u00f6nnen bzw. wie Migrant*innen selbst \u2013 beispielsweise durch Akteur*innen wie das Refugee Advisory Board (RAB) Germany oder die Vielzahl von Migrant*innenorganisationen\u2013 den Gesetzgebungsprozess beeinflussen k\u00f6nnen.

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Eine angemessene Beteiligung verschiedener Akteur*innen und eine gesellschaftspolitische Diskussion solch weitreichender Entscheidungen ist nicht nur demokratietheoretisch w\u00fcnschenswert, sondern letztlich auch f\u00fcr das Gelingen KI-gest\u00fctzter Verfahren entscheidend. Eine Vielzahl wissenschaftlicher Arbeiten hat bisherige \u2013 eher top-down initiierte \u2013 Bestrebungen, KI im Bereich Migration und Asyl einzusetzen, kritisch beleuchtet: etwa die Dialekterkennungssoftware des BAMF oder den Einsatz des Geomatch-Algorithmus in den Niederlanden, der mittlerweile bereits in der Pilotphase gestoppt wurde. Zuvor hatten Forschungsarbeiten auf die diskriminierenden Wirkweisen des zugrundeliegenden Algorithmus hingewiesen. Solche Systeme sind nicht nur mit Blick auf die Betroffenen h\u00f6chst problematisch und k\u00f6nnen zu Verletzungen von Grund- und Menschenrechten f\u00fchren, sondern k\u00f6nnen letztlich auch einen Reputationsschaden f\u00fcr die zust\u00e4ndigen Regierungen mit sich bringen.

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Dass KI und Digitalisierung globale Mobilit\u00e4t ma\u00dfgeblich ver\u00e4ndern und Chancen, Herausforderungen sowie Risiken f\u00fcr das Migrationsmanagement in der EU und Deutschland mit sich bringen, r\u00fcckt zunehmend in den Fokus wissenschaftlicher und gesellschaftspolitscher Debatten. Obwohl das KIMVG ein konkretes Beispiel daf\u00fcr ist, wie Gesetzgebung diese Chancen und Herausforderungen gestalten kann, findet die Auseinandersetzung bislang vor allem in Fachkreisen statt. In der breiteren \u00d6ffentlichkeit und den gro\u00dfen Medien wird der Entwurf bisher nur punktuell aufgegriffen. Das erschwert insbesondere Betroffenen \u2013 zus\u00e4tzlich zur juristischen Komplexit\u00e4t des Gesetzes \u2013 den Zugang zum Diskurs. Insgesamt macht der Entwurf deutlich, dass Fragen des KI-Einsatzes in der Migrations- und Asylverwaltung zweierlei ben\u00f6tigen: einen pr\u00e4zise formulierten und grundrechtskonformen rechtlichen Rahmen genauso wie eine grunds\u00e4tzliche gesellschaftliche Debatte dar\u00fcber, welchen Stellenwert KI und Automatisierungen in grundrechtssensiblen Verfahren haben sollten und ob und wie sie halten k\u00f6nnen, was sie versprechen.

\n

Eine englischsprachige, k\u00fcrzere Version dieses Posts wurde auf TechPolicy Press ver\u00f6ffentlicht.

","doi":"https://doi.org/10.59350/ydjk8-57942","guid":"https://fluchtforschung.net/?p=15944","language":"de","license":"https://creativecommons.org/licenses/by/4.0/legalcode","published_at":1788912000,"rid":"206na-z0869","summary":"Der Ende Juli verabschiedete Regierungsentwurf des KI-Migrationsverwaltungsgesetzes (KIMVG) will eine breite Rechtsgrundlage f\u00fcr den Einsatz von K\u00fcnstlicher Intelligenz (KI) in Visa-, Aufenthalts- und Asylverfahren schaffen.","tags":["Deutsch","Forschung","Asylverwaltung","Digitalisierung","Gesetzgebung"],"title":"Automatisierte Migrations- und Asylverwaltung? Der Gesetzesentwurf zum KIMVG auf dem Pr\u00fcfstand","updated_at":1789113416,"url":"https://fluchtforschung.net/automatisierte-migrations-und-asylverwaltung-der-gesetzesentwurf-zum-kimvg-auf-dem-pruefstand/","version":"v1"}},{"document":{"authors":[{"affiliation":[{"name":"Imperial College London, Chemstry"}],"contributor_roles":[],"family":"Rzepa","given":"Henry","url":"https://orcid.org/0000-0002-8635-8390"}],"blog":{"authors":[{"name":"Henry Rzepa","url":"https://orcid.org/0000-0002-8635-8390"}],"community_id":"8fb94c86-e95f-41cf-aac2-a2877ffc1b5f","created":1693094400,"current_feed_url":null,"description":"Chemistry with a twist","doi":"https://doi.org/10.59350/rzepa","favicon":"https://rogue-scholar.org/api/communities/8fb94c86-e95f-41cf-aac2-a2877ffc1b5f/logo","feed_format":"application/atom+xml","feed_url":"https://www.ch.ic.ac.uk/rzepa/blog/?feed=atom","filter":null,"generator":"WordPress","home_page_url":"https://www.ch.ic.ac.uk/rzepa/blog","issn":null,"language":"eng","license":"https://creativecommons.org/licenses/by/4.0/legalcode","prefix":"10.59350","relative_url":null,"secure":true,"slug":"rzepa","status":"active","subfield":"1606","title":"Henry Rzepa's Blog","updated":1789034499,"use_api":true},"blog_name":"Henry Rzepa's Blog","blog_slug":"rzepa","content_html":"
\n

A recently published article addresses[1] the long standing problem of why transition metals complexes such as e.g. Cp2TiCl2 in the presence of solutions of polysulfide dianions containing sulfur chains of various lengths, can react to form sulfur ring complexes of a specific size, depending on the metal. Thus when the early transition metal is Ti (Cp = cyclopentadienyl) it forms only the six membered ring shown below (X=S), with none of the five-membered/four-sulfur ring present. However, other central and later transition period metals only form four-sulfur rings.[1]
\n\"\"
\nThe effect was attributed to the degree of overlap\u00a0of a localised sulfur p-orbital with a vacant Ti d-orbital as shown below (Figure 1. click on the diagram to get a 3D model).

\n

\n

\"\"
\nFigure 1. Overlap between a sulfur p-donor and a titanium d-acceptor.

\n

One quantative estimate of the magnitude of the effect can be obtained using the NBO7 method[2], which provides a value for the perturbation interaction energy between the filled donor orbital (the S p-orbital) and the empty acceptor orbital (the Ti d-orbital) as a so-called E(2) energy. Thus in the article[1] the E(2) energy for the Ti six-membered complex shown above was reported as 21.2 kcal/mol (Table below) whereas for the analogous five-ring (for which the overlap between the two orbitals is less good) the value was 11.0 kcal/mol. This effect can be related [1] to the relative (free energy) stability of the product complex in the above reaction.

\n

The question now arises whether the effect can be “optimised” by changing some of the ring atoms from S to another. In fact eight crystal structures have been reported with such substitutions (Table) and so here the NBO7 analysis is repeated for these systems and a few other as yet unreported examples.

\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n
Table. NBO7 E(2) interaction energy for variants of Cp2TiS5.
CSD NameRing atomsNBO7 E(2)Ti-S length, \u00c5Ti-S dihedralLit/CSDMN15L/Def2-QZVPP NBO7
CYPTIS01S, S, S, S, S21.202.466, 2.47062.0[3][4]
KIVTOYS, S, Se, Se, Se21.702.47165.7[5][6]
NIRXERS, S, X=N-Me (ax)\u2020, S, S15.352.462, 2.47954.9[7], [8][9]
UnknownS, S, X=P-Me (ax), S, S23.592.45363.5unknown[10]
SEDRUOS, S, X=As-Me(ax), S, S23.492.45465.7[11][12]
SEDRUOS, S, X=As-Me(eq), S, S21.582.460, 2.47064.8\u2020[13]
FEHTOBS, S, X=Cp2TiS5, S, S\u20212.46368.9, 63.9[14][15]
VOSMUOS, S, Se, Se, Se21.702.47265.7[5], [16][17]
VOSNEZS, S,Se, Se, S19.932.463, 2.47565.1, 64.1[5], [18][19]
VOSNAVSe,Se,Se,Se,Se21.38–66.2[20],[21][22]
ZEMXIVS, Se, Se, Se, Se18.652.46767.0[23][24]
\n

Analysis

\n
    \n
  1. There appears to be a reasonable correction between the NBO E(2) energy and the Ti-S bond length. The shortest bond (X=PMe) corresponds to the highest E(2) value of 23.59 kcal/mol. SEDRUO is a known example (X=AsMe, Figure 2) and X=PMe is worthy of synthesis to reinforce this conclusion.
    2. \n
  2. The donation from the sulfur\u00a0p-orbital to the Ti d-orbital appears to reach a maximum at\u00a0~65\u00b0, not far off the value for Cp2TiS5 itself (Figure 1).
    3. \n
  3. The series\u00a0X=NMe, PMe, AsMe is interesting because the Me group has a favoured axial position (Figure 2), by an estimated 10.6 kcal/mol for\u00a0X=NMe. This remarkable preference is probably caused by the bond angle subtended at X, since no strong stereoelectronic effect could be found\u00a0(such as donation from the lone pair on the N/P/As).
    \n\"\"
    \nFigure 2.Structure of SEDRUO, showing the strong axial preference.
    4. \n
  4. X = Cp2TiS5 is interesting because it should exhibit the effect twice, at each Ti. Unfortunately the wavefunction for this species appears to have a pathological problem with converging to an NBO localised solution – we hope to find a solution to this at some stage. The Ti-S bond lengths however do not suggest the effect noted above will be especially high for this species.
    5. \n
  5. PUJFUV[25] replaces one six-electron Cp ligand metal donor with an apparent two-electron contribution from an 2,6-di-isopropylphenoxy ligand. This has a measured Ti-O bond length of 1.795\u00c5, which is towards the shorter end of the spectrum of Ti-O lengths (which range from ~1.7 to ~2.2\u00c5). This intriguing example will be analysed in a separate post.
    6. \n
\n

Conclusions

\n

The effect identified previously[1] which is responsible for the preference of early transition metals such as Ti to form polysulfide rings with five sulfurs rather than four appears to reach a maximum for the known species X=AsMe (Figure 2) or the as yet unmade molecule with X=PMe.

\n
\n

\u2020The equatorial isomer for X=NMe is a remarkable ~10.6 kcal/mol higher in free energy.[26] whereas for X=AsMe it is reduced to 4.59 kcal/mol. This is probably due to the angle subtended at N/As, which is 117.7\u00b0 for N and 103.6\u00b0 for As, which may also propagate to the values of the dihedral angle. \u2021The NBO7 localisation search terminated unsuccessfully after considering 100000 bonding patterns.

\n

References

\n
  1. H.S. Rzepa, and J.D. Woollins, \"Identifying the origins of the ring-size specificity of transition metals for polysulfide anions\", Dalton Transactions, 2026. https://doi.org/10.1039/d6dt01849a\n\n
    2. \n
  2. E.D. Glendening, C.R. Landis, and F. Weinhold, \"6 Natural bond orbital theory: Discovering chemistry with NBO7\", Complementary Bonding Analysis, pp. 129-156, 2021. https://doi.org/10.1515/9783110660074-006\n\n
    3. \n
  3. E. Muller, J.L. Petersen, and L.F. Dahl, \"Synthesis and characterization of Di-\u03c0-cyclopentadienyl- metal pentasulfides of titanium(IV) and vanadium (IV):an operational test of the influence of an unpaired electron on the molecular geometry\", Journal of Organometallic Chemistry, vol. 111, pp. 91-112, 1976. https://doi.org/10.1016/s0022-328x(00)87061-8\n\n
    4. \n
  4. H. Rzepa, \"CYPTIS5 MN15L/Def2-TZVPP, G = -3227.141839 Def2-QZVPP NBO\", 2026. https://doi.org/10.14469/hpc/15689\n\n
    5. \n
  5. P. Pekonen, Y. Hiltunen, R.S. Laitinen, and J. Valkonen, \"Selenium-77 NMR spectroscopic and x-ray crystallographic characterization of bis(cyclopentadienyl)titanium selenide sulfide mixtures [Ti(C5H5)2SexS5x]\", Inorganic Chemistry, vol. 30, pp. 1874-1878, 1991. https://doi.org/10.1021/ic00008a036\n\n
    6. \n
  6. H. Rzepa, \"KIVTOY MN15L/Def2-TZVPP DCM => NBO7 Def2-QZVPP\", 2026. https://doi.org/10.5281/zenodo.22270368\n\n
    7. \n
  7. R. Steudel, O. Schumann, J. Buschmann, and P. Luger, \"S4NR (R=Methyl,n-Octyl) as Novel Chelating Ligands in Titanocene Complexes and First Synthesis of Small Sulfurimide Heterocycles SnNR (n=5, 6)\", Angewandte Chemie International Edition, vol. 37, pp. 492-494, 1998. https://doi.org/10.1002/(sici)1521-3773(19980302)37:4<492::aid-anie492>3.0.co;2-a\n\n
    8. \n
  8. Steudel, R.., Schumann, O.., Buschmann, J.., and Luger, P.., \"CCDC 103650: Experimental Crystal Structure Determination\", 1998. https://doi.org/10.5517/cc3gvky\n\n
    9. \n
  9. H. Rzepa, \"NIRXER NBO7 Def2-QZVPP No solvent LP ( 2) S 4 88. BD*( 2)Ti 1- S 2 15.35\", 2026. https://doi.org/10.5281/zenodo.22141983\n\n
    10. \n
  10. H. Rzepa, \"SEDRUO (As-Me) => P-Me ax G = -3210.173356 Def2-QZVPP NBO7 LP ( 2) S 5 . BD*( 2)Ti 1- S 6 23.59\", 2026. https://doi.org/10.5281/zenodo.22664179\n\n
    11. \n
  11. R. Steudel, B. Holz, and J. Pickardt, \"Synthesis and Structure of [(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>TiS<sub>4</sub>AsCH<sub>3</sub>]\u2014a New Reagent for the Synthesis of Sulfur\u2010Rich Heterocycles\", Angewandte Chemie International Edition in English, vol. 28, pp. 1269-1271, 1989. https://doi.org/10.1002/anie.198912691\n\n
    12. \n
  12. H. Rzepa, \"SEDRUO (As-Me) NBO7 LP ( 2) S 5 BD*( 2)Ti 1- S 6 23.49\", 2026. https://doi.org/10.5281/zenodo.22286648\n\n
    13. \n
  13. H. Rzepa, \"SEDRUO (As-Me) eq NBO7 => Def2-QZVPP LP ( 2) S 4 101. BD*( 2)Ti 1- S 2 21.58\", 2026. https://doi.org/10.5281/zenodo.22669613\n\n
    14. \n
  14. D.M. Giolando, T.B. Rauchfuss, A.L. Rheingold, and S.R. Wilson, \"Chemistry of (RC5H4)2TiE5 (E = S, Se). New information on its reactions with nucleophiles, syntheses and reactions of 1,4-[(RC5H4)2Ti]2E4, and a second isomer of (RC5H4)2TiS2C2(CO2Me)2\", Organometallics, vol. 6, pp. 667-675, 1987. https://doi.org/10.1021/om00146a040\n\n
    15. \n
  15. H. Rzepa, \"FEHTOB Cp2Ti(SS)2TiCp2 NBO7 TZVPP\", 2026. https://doi.org/10.5281/zenodo.22655433\n\n
    16. \n
  16. Laasonen, Heli., Ik\u00e4heimonen, Johanna., Suomela, Mikko., Rautiainen, J. Mikko., and Laitinen, Risto S.., \"CCDC 1887988: Experimental Crystal Structure Determination\", 2019. https://doi.org/10.5517/ccdc.csd.cc21clvw\n\n
    17. \n
  17. H. Rzepa, \"VOSMUO NBO7 Def2-QZVPP no solvent LP ( 2) S 2 116. BD*( 2)Ti 1- S 6 21.70\", 2026. https://doi.org/10.5281/zenodo.22141977\n\n
    18. \n
  18. Laasonen, Heli., Ik\u00e4heimonen, Johanna., Suomela, Mikko., Rautiainen, J. Mikko., and Laitinen, Risto S.., \"CCDC 1887990: Experimental Crystal Structure Determination\", 2019. https://doi.org/10.5517/ccdc.csd.cc21clxy\n\n
    19. \n
  19. H. Rzepa, \"VOSNEZ MN15L/Def2-TZVPP DCM\", 2026. https://doi.org/10.5281/zenodo.22270375\n\n
    20. \n
  20. H. Laasonen, J. Ik\u00e4heimonen, M. Suomela, J.M. Rautiainen, and R.S. Laitinen, \"Titanocene Selenide Sulfides Revisited: Formation, Stabilities, and NMR Spectroscopic Properties\", Molecules, vol. 24, pp. 319, 2019. https://doi.org/10.3390/molecules24020319\n\n
    21. \n
  21. Laasonen, Heli., Ik\u00e4heimonen, Johanna., Suomela, Mikko., Rautiainen, J. Mikko., and Laitinen, Risto S.., \"CCDC 1887989: Experimental Crystal Structure Determination\", 2019. https://doi.org/10.5517/ccdc.csd.cc21clwx\n\n
    22. \n
  22. H. Rzepa, \"VOZNAV MN15L/Def2-QZVPP (Se only) NBO7 LP ( 2)Se 2 BD*( 2)Ti 1-Se 6 21.38\", 2026. https://doi.org/10.5281/zenodo.22286621\n\n
    23. \n
  23. C.P. Raptopoulou, A. Terzis, N. Tzavellas, and N. Klouras, \"Sulfur\u2010Selenium Chelates: Crystal structure of the first titanocene derivative Ti(\u03b7<sup>5</sup>\u2010C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>SSe<sub>4</sub>\", Zeitschrift f\u00fcr anorganische und allgemeine Chemie, vol. 621, pp. 1800-1802, 1995. https://doi.org/10.1002/zaac.19956211032\n\n
    24. \n
  24. H. Rzepa, \"ZEMXIY NBO7 Def2-QZVPP No solvent LP ( 2)Se 3 124. BD*( 2)Ti 1- S 2 18.65\", 2026. https://doi.org/10.5281/zenodo.22141970\n\n
    25. \n
  25. A.V. Firth, and D.W. Stephan, \"Monocyclopentadienyl\u2212Titanium Aryloxide Sulfide Complexes\", Inorganic Chemistry, vol. 37, pp. 4726-4731, 1998. https://doi.org/10.1021/ic9800839\n\n
    26. \n
  26. H. Rzepa, \"NIRXER Def2-TZVPP, DCM equatorial N-Me G = -2923.496304 (G = -2923.513188) DG = 10.6\", 2026. https://doi.org/10.5281/zenodo.22669635\n\n
    27. \n
\n\n
","doi":"https://doi.org/10.59350/p8zwp-39q65","guid":"https://www.ch.ic.ac.uk/rzepa/blog/?p=31892","language":"en","license":"https://creativecommons.org/licenses/by/4.0/legalcode","published_at":1788998400,"reference":[{"id":"https://doi.org/10.1039/d6dt01849a","unstructured":"Rzepa, H. S., & Woollins, J. D. (2026). Identifying the origins of the ring-size specificity of transition metals for polysulfide anions. Dalton Transactions."},{"id":"https://doi.org/10.1515/9783110660074-006","unstructured":"Glendening, E. D., Landis, C. R., & Weinhold, F. (2021). 6 Natural bond orbital theory: Discovering chemistry with NBO7. In Complementary Bonding Analysis (pp. 129\u2013156). De Gruyter."},{"id":"https://doi.org/10.1016/s0022-328x(00)87061-8","unstructured":"Muller, E. G., Petersen, J. L., & Dahl, L. F. (1976). Synthesis and characterization of Di-\u03c0-cyclopentadienyl- metal pentasulfides of titanium(IV) and vanadium (IV):an operational test of the influence of an unpaired electron on the molecular geometry. Journal of Organometallic Chemistry, 111(1), 91\u2013112."},{"id":"https://doi.org/10.14469/hpc/15689","unstructured":"Rzepa, H., Imperial College London, Imperial College Research Computing Service, & Rzepa, H. (2026). CYPTIS5 MN15L/Def2-TZVPP, G = -3227.141839 Def2-QZVPP NBO [Dataset]. Imperial College London."},{"id":"https://doi.org/10.1021/ic00008a036","unstructured":"Pekonen, P., Hiltunen, Y., Laitinen, R. S., & Valkonen, J. (1991). Selenium-77 NMR spectroscopic and x-ray crystallographic characterization of bis(cyclopentadienyl)titanium selenide sulfide mixtures [Ti(C5H5)2SexS5x]. Inorganic Chemistry, 30(8), 1874\u20131878."},{"id":"https://doi.org/10.5281/zenodo.22270368","unstructured":"Rzepa, H. (2026). KIVTOY MN15L/Def2-TZVPP DCM => NBO7 Def2-QZVPP [Dataset]. Zenodo."},{"id":"https://doi.org/10.1002/(sici)1521-3773(19980302)37:4492::aid-anie4923.0.co;2-a","unstructured":"R. Steudel, O. Schumann, J. Buschmann, and P. Luger, \"S4NR (R=Methyl,n-Octyl) as Novel Chelating Ligands in Titanocene Complexes and First Synthesis of Small Sulfurimide Heterocycles SnNR (n=5, 6)\", Angewandte Chemie International Edition, vol. 37, pp. 492-494, 1998. https://doi.org/10.1002/(sici)1521-3773(19980302)37:4<492::aid-anie492>3.0.co;2-a"},{"id":"https://doi.org/10.5517/cc3gvky","unstructured":"Steudel, R., Schumann, O., Buschmann, J., & Luger, P. (1998). CCDC 103650: Experimental Crystal Structure Determination [Dataset]. Cambridge Crystallographic Data Centre."},{"id":"https://doi.org/10.5281/zenodo.22141983","unstructured":"Rzepa, H. (2026). NIRXER NBO7 Def2-QZVPP No solvent LP ( 2) S 4 88. BD*( 2)Ti 1- S 2 15.35 [Dataset]. Zenodo."},{"id":"https://doi.org/10.5281/zenodo.22664179","unstructured":"Rzepa, H. (2026). SEDRUO (As-Me) => P-Me ax G = -3210.173356 Def2-QZVPP NBO7 LP ( 2) S 5 . BD*( 2)Ti 1- S 6 23.59 [Dataset]. Zenodo."},{"id":"https://doi.org/10.1002/anie.198912691","unstructured":"Steudel, R., Holz, B., & Pickardt, J. (1989). Synthesis and Structure of [(C5H5)2TiS4AsCH3]\u2014a New Reagent for the Synthesis of Sulfur\u2010Rich Heterocycles. Angewandte Chemie International Edition in English, 28(9), 1269\u20131271."},{"id":"https://doi.org/10.5281/zenodo.22286648","unstructured":"Rzepa, H. (2026). SEDRUO (As-Me) NBO7 LP ( 2) S 5 BD*( 2)Ti 1- S 6 23.49 [Dataset]. Zenodo."},{"id":"https://doi.org/10.5281/zenodo.22669613","unstructured":"Rzepa, H. (2026). SEDRUO (As-Me) eq NBO7 => Def2-QZVPP LP ( 2) S 4 101. BD*( 2)Ti 1- S 2 21.58 [Dataset]. Zenodo."},{"id":"https://doi.org/10.1021/om00146a040","unstructured":"Giolando, D. M., Rauchfuss, T. B., Rheingold, A. L., & Wilson, S. R. (1987). Chemistry of (RC5H4)2TiE5 (E = S, Se). New information on its reactions with nucleophiles, syntheses and reactions of 1,4-[(RC5H4)2Ti]2E4, and a second isomer of (RC5H4)2TiS2C2(CO2Me)2. Organometallics, 6(3), 667\u2013675."},{"id":"https://doi.org/10.5281/zenodo.22655433","unstructured":"Rzepa, H. (2026). FEHTOB Cp2Ti(SS)2TiCp2 NBO7 TZVPP [Dataset]. Zenodo."},{"id":"https://doi.org/10.5517/ccdc.csd.cc21clvw","unstructured":"Laasonen, H., Ik\u00e4heimonen, J., Suomela, M., Rautiainen, J. M., & Laitinen, R. S. (2019). CCDC 1887988: Experimental Crystal Structure Determination [Dataset]. Cambridge Crystallographic Data Centre."},{"id":"https://doi.org/10.5281/zenodo.22141977","unstructured":"Rzepa, H. (2026). VOSMUO NBO7 Def2-QZVPP no solvent LP ( 2) S 2 116. BD*( 2)Ti 1- S 6 21.70 [Dataset]. Zenodo."},{"id":"https://doi.org/10.5517/ccdc.csd.cc21clxy","unstructured":"Laasonen, H., Ik\u00e4heimonen, J., Suomela, M., Rautiainen, J. M., & Laitinen, R. S. (2019). CCDC 1887990: Experimental Crystal Structure Determination [Dataset]. Cambridge Crystallographic Data Centre."},{"id":"https://doi.org/10.5281/zenodo.22270375","unstructured":"Rzepa, H. (2026). VOSNEZ MN15L/Def2-TZVPP DCM [Dataset]. Zenodo."},{"id":"https://doi.org/10.3390/molecules24020319","unstructured":"Laasonen, H., Ik\u00e4heimonen, J., Suomela, M., Rautiainen, J. M., & Laitinen, R. S. (2019). Titanocene Selenide Sulfides Revisited: Formation, Stabilities, and NMR Spectroscopic Properties. Molecules, 24(2), 319."},{"id":"https://doi.org/10.5517/ccdc.csd.cc21clwx","unstructured":"Laasonen, H., Ik\u00e4heimonen, J., Suomela, M., Rautiainen, J. M., & Laitinen, R. S. (2019). CCDC 1887989: Experimental Crystal Structure Determination [Dataset]. Cambridge Crystallographic Data Centre."},{"id":"https://doi.org/10.5281/zenodo.22286621","unstructured":"Rzepa, H. (2026). VOZNAV MN15L/Def2-QZVPP (Se only) NBO7 LP ( 2)Se 2 BD*( 2)Ti 1-Se 6 21.38 [Dataset]. Zenodo."},{"id":"https://doi.org/10.1002/zaac.19956211032","unstructured":"Raptopoulou, C. P., Terzis, A., Tzavellas, N., & Klouras, N. (1995). Sulfur\u2010Selenium Chelates: Crystal structure of the first titanocene derivative Ti(\u03b75\u2010C5H5)2SSe4. Zeitschrift F\u00fcr Anorganische Und Allgemeine Chemie, 621(10), 1800\u20131802."},{"id":"https://doi.org/10.5281/zenodo.22141970","unstructured":"Rzepa, H. (2026). ZEMXIY NBO7 Def2-QZVPP No solvent LP ( 2)Se 3 124. BD*( 2)Ti 1- S 2 18.65 [Dataset]. Zenodo."},{"id":"https://doi.org/10.1021/ic9800839","unstructured":"Firth, A. V., & Stephan, D. W. (1998). Monocyclopentadienyl\u2212Titanium Aryloxide Sulfide Complexes. Inorganic Chemistry, 37(18), 4726\u20134731."},{"id":"https://doi.org/10.5281/zenodo.22669635","unstructured":"Rzepa, H. (2026). NIRXER Def2-TZVPP, DCM equatorial N-Me G = -2923.496304 (G = -2923.513188) DG = 10.6 [Dataset]. Zenodo."}],"rid":"qpjc6-7hm46","summary":"A recently published article addresses the long standing problem of why transition metals complexes such as e.g. Cp2TiCl2 in the presence of solutions of polysulfide dianions containing sulfur chains of various lengths, can react to form sulfur ring complexes of a specific size, depending on the metal.","tags":["Interesting Chemistry","Reaction Mechanism"],"title":"Identifying the origins of the ring-size specificity of transition metals for polysulfide anions: \"tuning\" the effect.","updated_at":1789111825,"url":"https://www.ch.ic.ac.uk/rzepa/blog/?p=31892","version":"v1"}},{"document":{"authors":[{"affiliation":[{"name":"University of Wroc\u0142aw, Chemistry"}],"contributor_roles":[],"family":"Janeta","given":"Mateusz","url":"https://orcid.org/0000-0003-2197-7913"}],"blog":{"authors":null,"community_id":"c21eed24-c860-43d0-997c-0bc782922544","created":1788652800,"current_feed_url":null,"description":null,"doi":"https://doi.org/10.59350/silsesquioxane","favicon":"https://rogue-scholar.org/api/communities/c21eed24-c860-43d0-997c-0bc782922544/logo","feed_format":"application/atom+xml","feed_url":"https://silsesquioxane.blogspot.com/feeds/posts/default","filter":null,"generator":"Blogger","home_page_url":"https://silsesquioxane.blogspot.com/","issn":null,"language":"eng","license":"https://creativecommons.org/licenses/by/4.0/legalcode","prefix":"10.59350","relative_url":null,"secure":true,"slug":"silsesquioxane","status":"active","subfield":"1604","title":"Polyhedral Oligomeric Silsesquioxane (POSS) Chemistry","updated":1789050682,"use_api":true},"blog_name":"Polyhedral Oligomeric Silsesquioxane (POSS) Chemistry","blog_slug":"silsesquioxane","content_html":"
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Polyhedral oligomeric silsesquioxanes (POSS) have long served as more than a hybrid organic-inorganic filler for polymers. Their partially condensed silanol forms present a rigid, oxygen-rich pocket that closely resembles a fragment of amorphous silica, and this pocket is an excellent ligand for metal ions of nearly every part of the periodic table. Single-crystal X-ray diffraction has been the decisive tool for confirming what these metal-POSS assemblies actually look like, since spectroscopic and computational evidence alone can rarely distinguish between competing cage topologies. This review surveys recent crystallographically confirmed metal-POSS complexes, organized by the metal center, and closes with a synthesis of the structural trends that emerge once the diffraction data are compared side by side.

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POSS as a Ligand Platform for Metal Ions

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The starting point for nearly every metal-POSS complex discussed below is an incompletely condensed silsesquioxane, most often a trisilanol of general formula R7Si7O9(OH)3, in which R is a bulky organic substituent such as cyclohexyl, isobutyl, or phenyl.1 Deprotonation of the three remaining hydroxyl groups generates a trianionic, oxygen-donor pocket that reacts with a metal-organic precursor MR'n to cap the open corner of the cage, expelling the R' groups as volatile byproducts and leaving the metal bound in a fashion reminiscent of a tripodal ligand (Figure 1). Depending on the metal and its coordination requirements, this corner-capped unit can be a stable end point in its own right, as is typical for many main-group and alkaline-earth derivatives, or it can undergo further self-assembly into larger cage structures through bridging oxo, hydroxo, or alkoxo groups, as is the case for most of the transition metal and lanthanide complexes discussed below. Because these frameworks so closely mimic isolated surface sites on silica, they have functioned for decades as molecular models for silica-supported catalysts, and single-crystal X-ray diffraction has been essential for relating a given coordination geometry to catalytic behavior observed in solution or in the heterogeneous phase.

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\n\"Scheme\n

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Figure 1. General corner-capping strategy for forming a closed-cage metallasilsesquioxane from an open-cage trisilanol and a metal-organic precursor MR'n, where M is a metal from group 1, 2, or 13 of the periodic table, R is an unreactive alkyl or aryl substituent, and R' is an alkyl group or hydrogen.

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Nickel, Manganese, Iron, and Vanadium Cages

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Beyond copper, the same cage-forming chemistry has been extended to several other transition metals, each contributing distinctive structural motifs. A hexanuclear nickel(II) phenylsilsesquioxane, isolated as a dioxane-benzonitrile-water solvate and studied by X-ray and topological analysis, adopts an unusual cylinder-like architecture in which benzonitrile coordinates directly to the metallasilsesquioxane core, a rare mode of complexation for this ligand class.14 This complex was also tested as a catalyst for oxidations with peroxides: tert-butyl hydroperoxide converted 1-phenylethanol to acetophenone in 90 percent yield after 24 hours, whereas meta-chloroperoxybenzoic acid oxidized cyclohexane to a cyclohexanone/cyclohexanol mixture in a more modest 24 percent yield, with methylcyclohexane giving a broader spread of isomeric ketones and alcohols in comparable overall yield.14

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Figure 2. X-ray crystal structure of the cylinder-like Ni6 architecture of Bilyachenko et al., Molecules 2016, 21, 665 (ref. 14), rendered directly from the deposited crystal structure. Top view (left) shows the Ni1, Ni2, and Ni3 pairs forming the Ni6O6 ring sandwiched between the two 12-membered siloxane cycles, with the encapsulated chloride anion at the crystallographic center of inversion. Side view (right) shows the resulting cylinder shape, alongside a detail of the distorted octahedral coordination environment at one nickel center.

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Manganese chemistry has produced an especially structurally diverse series, beginning with the first heterobimetallic Mn/Na and Mn/Li derivatives reported by Lorenz, Blaurock, and Edelmann in 2008, both confirmed by single-crystal X-ray diffraction with manganese-oxygen bond lengths of 1.985(2) to 2.146(2) angstroms in the Mn/Na cage and a narrower 2.046(3) to 2.048(3) angstrom range in the Mn/Li cage. This early series was purely structural in purpose and was reported without any catalytic testing.15 More recent manganese cages incorporating 1,10-phenanthroline or bathophenanthroline ligands have revealed a still more unusual feature, the coexistence of sodium, manganese(II), and manganese(III) within a single cage, a consequence of spontaneous oxidation during self-assembly that only diffraction analysis could unambiguously confirm, with the manganese(III)-oxygen bonds consistently 0.2 to 0.3 angstroms shorter than the corresponding manganese(II)-oxygen bonds in the same cage.16,17 The phenanthroline series was synthesized specifically to evaluate manganese silsesquioxanes as precatalysts for the oxidative amidation of alcohols and aldehydes with tert-butyl hydroperoxide, and at 5 mol percent manganese loading the two simplest cages in the series gave the benzamide product in 84 and 79 percent yield, outperforming a range of simple manganese salts and oxides tested for comparison.16 The bathophenanthroline series was instead developed as a catalyst for the solvent-free cycloaddition of CO2 to epoxides, reaching a 90 percent yield of cyclic carbonate under standard conditions and up to 99 percent yield after optimizing the reaction temperature and pressure, roughly double the yield obtained with simple manganese chloride under the same conditions, and the same complexes additionally showed antifungal activity against several phytopathogenic Fusarium and related fungal species that exceeded that of the commercial fungicide triadimefon at equal concentration.17 Iron(III)-based phenylsilsesquioxane/acetylacetonate complexes reported in 2024 show a comparable sensitivity to the identity of the alkali metal template, with lithium, sodium, and potassium each directing the assembly toward a distinct cage size and silsesquioxane ring size, including the first observation of a trimeric silsesquioxane ligand within a metallasilsesquioxane cage.18 Catalytically, the Fe4Na4 congener stood out among the three, reaching a record 55 percent yield of oxygenates in the peroxidative oxidation of cyclohexane, and the series as a whole also promoted the cycloaddition of CO2 to epoxides, giving cyclic carbonates in 58 to 96 percent yield depending on the substrate.18

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Figure 3 (Fe4Na4 and Fe3K3 renders pending). X-ray crystal structure of the Fe2Li2 cage from the alkali-metal-dependent series of Bilyachenko et al., Inorg. Chem. 2024, 63, 1909-1918 (ref. 18), rendered directly from the deposited crystallographic coordinates (CCDC 2263801). The Fe4Na4 (CCDC 2267402) and Fe3K3 (CCDC 2280386) congeners from the same series will be added as companion panels once rendered.

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Vanadium chemistry has taken a different direction altogether, yielding polyoxovanadate clusters protected by silsesquioxane ligands rather than classical cage metallasilsesquioxanes. A fourteen-vanadium cluster represents the highest nuclearity yet reported for this combination, displaying vanadium-oxygen distances of 1.933 to 2.071 angstroms to the silsesquioxane ligands and considerably shorter terminal vanadium-oxo bonds of 1.519 to 1.695 angstroms, while a six-vanadium congener adopts a more regular planar hexagonal arrangement with vanadium-oxygen bonds of 1.987 to 2.006 angstroms and terminal vanadium-oxo bonds of 1.562 to 1.601 angstroms.19 The hexavanadium cluster was developed specifically as a heterogeneous catalyst for the synthesis of quinazolinones from 2-aminobenzamide and aldehydes, reaching essentially complete conversion with selectivity typically between 90 and 99 percent across a broad substrate scope of electron-rich, electron-poor, heterocyclic, and aliphatic aldehydes, and it clearly outperformed the higher-nuclearity fourteen-vanadium cluster under comparable conditions. The catalyst could be recycled for at least six successive runs with only a negligible loss of conversion and a slight decrease in selectivity, and inductively coupled plasma mass spectrometry confirmed that no more than 0.015 percent of the vanadium content leached into solution during the reaction, supporting its heterogeneous mode of action.

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Zinc-POSS Complexes: Structure and Applications in Catalysis

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Zinc occupies a smaller but catalytically significant niche within this literature. Di Iulio, Jones, Mahon, and Apperley reported in 2010 the first structurally characterized zinc(II) silsesquioxane complexes, describing their solid-state structures as unprecedented at the time and evaluating the resulting compounds as initiators for the ring-opening polymerization of rac-lactide.20 A structurally distinct approach was taken in our own work on an imine-functionalized POSS ligand, in which the silsesquioxane core and the steric bulk of the imine side arms direct the formation of a tetrazinc complex, denoted Zn4@POSS-1, whose solid-state structure was established by X-ray crystallography alongside an extensive spectroscopic characterization in solution.21 The four zinc centers adopt a distorted tetrahedral geometry, two with a delta and two with a lambda configuration, with Zn-O bond lengths of 1.914(5) to 1.924(4) angstroms and Zn-N bond lengths of 1.979(6) to 2.016(5) angstroms, both ranges comparable to typical Zn(II) Schiff-base complexes, while the silicon-oxygen-silicon angles within the POSS core widen to between 139.6(3) and 167.3(3) degrees at the corners capped by the zinc centers. Zn4@POSS-1 is also structurally distinctive within the broader body of work surveyed in this review. In most of the crystallographically confirmed complexes discussed above, from the copper, manganese, and iron cages to the nickel cylinder and the lanthanide and actinide clusters, the metal centers are encapsulated inside a closed cage, sandwiched between two silsesquioxane ligand planes or embedded within a bridging oxo core sitting at the heart of the assembly. Zn4@POSS-1 departs from this pattern: the four zinc centers are held on the outside of an open, partially condensed POSS scaffold, each capped by one arm of the imine-functionalized ligand rather than being enclosed within a fully closed double-decker or sandwich core. This places Zn4@POSS-1 closer in spirit to the corner-capping assembly mode described for the main-group and alkaline-earth derivatives later in this review, in which a metal center caps an open corner of the cage from the outside, than to the encapsulated, internally templated architectures that dominate the transition-metal and lanthanide chemistry surveyed elsewhere in this article. This complex proved effective as a multisite catalyst for the cycloaddition of CO2 with epoxides to form cyclic carbonates under low CO2 pressure, a transformation of considerable interest for carbon utilization chemistry, and it illustrates how the same coordination chemistry that produces striking copper and manganese cages can be redirected toward small-molecule catalysis when a redox-inactive metal such as zinc is used instead. With styrene oxide as the model substrate, tetrabutylammonium iodide as co-catalyst, and 1 atmosphere of CO2 at 100 degrees Celsius, the catalyst alone was inactive, but the Zn4@POSS-1/TBAI pair reached 96 percent conversion to styrene carbonate at a turnover frequency of 25 per hour, rising to 98 percent conversion at 130 degrees Celsius, and it retained a useful 95 percent conversion even at a ten-fold lower catalyst loading when the reaction time was extended.21

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Figure 4. X-ray crystal structure of Zn4@POSS-1 from Janeta, Lis, Szafert, Chem. Eur. J. 2020, 26, 13686-13697 (ref. 21), rendered directly from the deposited crystal structure (CCDC 1504223). The imine-functionalized POSS core is capped by four Zn(II) centers, each chelated by an N,N-imine side arm in the meso-(delta,delta,lambda,lambda) configuration described in the text.

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Lanthanide and Actinide Metallasilsesquioxanes: Magnetism and Luminescence

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Lanthanide-based metallasilsesquioxanes form a comparatively young but fast-moving subfield, motivated by the combination of structural novelty with magnetic and luminescent function. The first CeIV metallasilsesquioxane complex, reported by Gun'ko, Reilly, Edelmann, and Schmidt in 2001, established that even a large, high-valent lanthanide ion could be accommodated within a silsesquioxane coordination environment.22 Lorenz and coworkers subsequently reported an erbium complex in which two silsesquioxane cages become coupled through a bridging siloxy unit, a transformation that had not previously been observed for a lanthanide-templated system.23 Since 2020, a series of tetranuclear cage-like lanthanide silsesquioxanes built around a prism-like Ln4 core has produced some of the most functionally interesting examples in the entire field. Terbium and europium derivatives display the first luminescence reported for a cage-like lanthanide silsesquioxane, and one terbium-based cage additionally exhibits a magnetic spin-flip transition.24

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Figure 5. X-ray crystal structure of the mixed-lanthanide cage anion of (Et4N)2[(PhSiO1.5)8(Y0.75Dy0.25O1.5)4(O)(NO3)6(EtOH)2(MeCN)2], compound 1 of Kulakova et al., Eur. J. Inorg. Chem. 2021, 2696-2701 (ref. 26), CCDC 2062487, rendered directly from the deposited crystallographic coordinates. Two parallel tetraphenylcyclotetrasiloxanolate macrocycles sandwich a distorted-square (Y0.75Dy0.25O1.5)4 core (left). The tetraethylammonium counter-cation is shown alongside the cage in the side view (right). This is the compound that displays field-induced single-molecule magnet behavior in addition to the characteristic dysprosium green-yellow emission.

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Figure 6. X-ray crystal structure of the homometallic cage anion of (Ph4P)2[(PhSiO1.5)8(DyO1.5)4(O)(NO3)6(EtOH)2(MeCN)2], compound 3 of Kulakova et al., Eur. J. Inorg. Chem. 2021, 2696-2701 (ref. 26), CCDC 2002355, rendered directly from the deposited crystallographic coordinates. The same prism-like topology as in Figure 5 is retained with four Dy(III) centers in the core (left). The tetraphenylphosphonium counter-cation is shown alongside the cage (right). Unlike the mixed Y/Dy analogue, this all-dysprosium cage and its tetraethylammonium salt (compound 2, CCDC 2002354, not shown) do not display slow relaxation of the magnetization, a difference attributed to magnetic interactions between the four Dy(III) centers.

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Related dysprosium and yttrium/dysprosium cages combine field-induced single-molecule magnet behavior with green-yellow emission, yielding the first bifunctional magneto-luminescent silsesquioxane reported in the literature, while mixed terbium/europium cages have been developed specifically as luminescent thermometers operating between 41 and 100 degrees Celsius through a temperature-dependent energy transfer between the two lanthanide centers.25,26 A further mixed-lanthanide series combining dysprosium, europium, terbium, and yttrium in various ratios extends this dual functionality: the dysprosium/europium member behaves as a field-induced single-molecule magnet, with an effective energy barrier of 11.3 wavenumbers under an applied direct-current field, while simultaneously operating as a europium-based emissive thermometer across the range of 293 to 373 kelvin, reaching a maximum relative thermal sensitivity of 1.15 percent per kelvin at 293 kelvin, whereas the terbium- and yttrium-containing congeners of the same series show neither slow magnetic relaxation nor temperature-dependent emission.27 At still higher nuclearity, a tridecanuclear gadolinium(III) cluster with an unprecedented body-centered cuboctahedron core represents the highest nuclearity yet reported for a lanthanide silsesquioxane and was synthesized specifically to explore cryogenic magnetic refrigeration, reaching a maximum magnetic entropy change of 20 joules per kilogram per kelvin at 2 kelvin under an applied field of 7.0 tesla.28 Actinide chemistry entered this field only recently, with Tricoire, Mazzanti, and coworkers reporting in 2024 the first trinuclear uranium(III) metallasilsesquioxane, a complex that exhibits magnetic exchange between the three uranium centers and promotes the reduction of dinitrogen in the presence of a reducing agent, with U-O bond lengths ranging from 2.125(16) to 2.568(17) angstroms and an average value of 2.36(2) angstroms.29

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Figure 7. X-ray crystal structure of the first trinuclear U(III) metallasilsesquioxane, [U3(iBuPOSS)3], of Tricoire et al., Chem. Commun. 2024, 60, 55-58 (ref. 29), rendered directly from the deposited crystallographic coordinates. The three uranium centers (U1, U2, U3) are arranged in a triangular U3(mu-O)6 core, each capped by one iBuPOSS ligand and linked to its neighbors by bridging siloxide oxygens, with U-O distances ranging from 2.125(16) to 2.568(17) angstroms and an average value of 2.36(2) angstroms, consistent with previously reported U(III) siloxide complexes.

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Main-Group and Alkaline-Earth Derivatives

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A smaller number of structurally confirmed metal-POSS complexes involve main-group or alkaline-earth elements rather than transition metals or f-block ions. Duchateau and coworkers prepared a family of tin-containing polyhedral oligometallasilsesquioxanes in 2004 starting from cyclopentyl-substituted silsesquioxane trisilanols. Protonolysis with a tin(II) amide gave three-coordinate Sn(II) dimers of the type [(cyclopentyl)7Si7O11(OX)Sn]2 (compound 2 shown below), which proved hydrolytically unstable and feature a planar, strained (SnO)2 four-membered ring with an O-Sn-O angle of 75.39(13) degrees and an Sn-O-Sn angle of 104.61(13) degrees, the bridging tin-oxygen bonds of 2.177(3) and 2.172(3) angstroms being noticeably longer than the terminal, sigma-bonded tin-oxygen bond of 1.995(3) angstroms, whereas reaction with Cl2Sn(acac)2 gave hydrolytically robust, octahedrally coordinated Sn(IV) mono-tin complexes. Slow hydrolysis of the corresponding tin(IV) chloride cluster instead produced an unprecedented anionic trimeric cluster (compound 6) in which three octahedral Sn(IV) centers are held together by three silsesquioxane cages and four bridging hydroxyl groups, three of them bridging two tin atoms and one bridging all three, with a triethylammonium counterion occupying the remaining corner of the resulting incomplete cube. In this cluster the average tin-oxygen-tin angle at the doubly bridging hydroxyls, 112.3(3) degrees, is noticeably wider than the corresponding angle at the triply bridging hydroxyl, 100.9(3) degrees, while the tin atoms are linked to the silsesquioxane cages by tin-oxygen-silicon bonds averaging 1.974(4) angstroms in length, with a tin-oxygen-silicon angle of about 140 degrees at the monodentate silsesquioxane linkages and about 134 degrees at the bidentate ones. Despite this structural sophistication, none of the tin(IV) complexes showed any catalytic activity when screened in the Baeyer-Villiger oxidation of cyclohexanone, the Oppenauer oxidation of isopropanol, or the epoxidation of cyclooctene, a result the authors attributed to the coordinative saturation and reduced Lewis acidity of the octahedral, and in one case anionic, tin centers.30

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Figure 8. Left: the anionic trinuclear Sn(IV) cluster {[(cyclopentyl)7Si7O12Sn]3(mu2-OH)3(mu3-OH)}-{HNEt3}+ (compound 6, CCDC 238581). Right: the three-coordinate Sn(II) dimer [(cyclopentyl)7Si7O11(OSiMe3)Sn]2 (compound 2, CCDC 238582), with a center of inversion in the planar (SnO)2 ring. Both structures from Duchateau et al., Dalton Trans. 2004, 2677-2682 (ref. 30), rendered directly from the deposited crystallographic coordinates.

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Lorenz, Blaurock, and Edelmann reported in the same period the first metallasilsesquioxane derivative of a heavier alkaline-earth metal, a dinuclear calcium complex in which two anionic silsesquioxane cages bridge a pair of unsymmetrically solvated calcium centers.31 Although these examples remain fewer in number than their transition metal and lanthanide counterparts, they demonstrate that the silsesquioxane cage can stabilize an unusually broad span of ionic radii and electronic configurations, from small trivalent tin to large, weakly coordinating alkaline-earth cations.

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Copper Cage Silsesquioxanes: The Dominant Family

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Copper accounts for the largest and most rapidly growing body of crystallographically confirmed metal-POSS chemistry, driven principally by the systematic work of Bilyachenko and coworkers. Across this family the recurring synthetic purpose was catalytic rather than purely structural, since nearly every reported cage was subsequently tested as a precatalyst for the peroxidative oxidation of light alkanes, cyclic hydrocarbons, and secondary alcohols with hydrogen peroxide or tert-butyl hydroperoxide, and crystallographic confirmation of the cage architecture was pursued specifically because catalytic performance was found to depend on the precise nuclearity and connectivity of the metal-oxo core rather than on solution composition alone.2,3,4,6,7,8,9,10,11,13

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The binuclear \"cooling tower\" complex [(PhSiO1.5)10(CuO)2(NaO0.5)2] reported in 2013 established the basic architecture of a copper-silsesquioxane cage, in which cyclic phenylsilsesquioxane ligands sandwich a small metal-oxo core, and its structure was confirmed by single-crystal X-ray diffraction, with copper-oxygen bond lengths of 1.906(3) to 1.956(4) angstroms and a silicon-oxygen-silicon bridging angle as wide as 166.2(3) degrees.2 The complex was synthesized specifically to probe alkane and alcohol oxidation catalysis, and in benzene oxidation with hydrogen peroxide and nitric acid as promoter it reached a turnover number of 550 and a product yield of up to 41 percent, while oxidation of 1-phenylethanol to acetophenone with tert-butyl hydroperoxide proceeded in a yield approaching 100 percent after four hours.

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Nonanuclear methylsilsesquioxane cages appeared in 2017, alongside trinuclear and hexanuclear congeners obtained from the same reaction system, each nuclearity and connectivity again established by diffraction, with mean copper-copper and copper-oxygen siloxanolate distances of 2.869(5) and 1.935(9) angstroms in the trinuclear cage.3 These complexes were likewise developed as alkane and alcohol oxidation catalysts, and the trinuclear cage converted 1-phenylethanol to acetophenone in 96 percent yield and cyclohexanol to cyclohexanone in 77 percent yield, while cyclohexane oxidation with hydrogen peroxide reached a total yield of 20 percent and a turnover number of 184, several times higher than the yield obtained with simple copper nitrate under the same conditions.

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A distinct nonanuclear phenylsilsesquioxane cage of Cu9Na6 composition, formed with the assistance of a phenanthroline ligand that does not itself enter the final structure, followed in 2018, together with an ionic Cu9Na4 congener obtained under related conditions.4 Both complexes were prepared as catalysts for the oxidative amidation of benzyl alcohol, a reaction in which the Cu9Na6 cage required only 100 parts per million of copper and reached a turnover number of 7700 and a turnover frequency of 325 per hour, substantially outperforming copper oxide alone under the same conditions, and it additionally converted cyclohexanone or acetophenone in 63 or 98 percent yield in alcohol oxidation with tert-butyl hydroperoxide.

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The coordinating role of the alkali metal cation proved to be a recurring structural variable rather than an incidental detail. Sandwich-like Cu4M2 complexes built around lithium, sodium, and potassium templates, distinguished crystallographically by intramolecular alkali metal to alkali metal separations ranging from 10.35 to 11.45 angstroms, were shown to direct the assembly toward distinct architectures even when the silsesquioxane and transition metal components were otherwise unchanged, although specific catalytic yields for this particular series were not reported in the accessible source text.5 The corresponding rubidium and cesium templated tetracopper cages, resolved crystallographically with rubidium to rubidium separations as long as 9.39 angstroms, were tested extensively as alkane oxidation and carboxylation catalysts, reaching a 35 percent yield and a turnover number of 320 in cyclohexane oxidation with hydrogen peroxide and a 50 percent total yield with a turnover number of 277 in the oxidative carboxylation of n-butane to a mixture of pentanoic acids, in addition to alcohol oxidations that converted 1-phenylethanol to acetophenone in 98 percent yield.6

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Heptanuclear cages bridged additionally by benzoate ligands were reported between 2019 and 2021, with the three linearly disposed copper centers in the cage subtending an angle of 178.04(2) degrees.7 The heptanuclear complex was again evaluated as an alkane and alcohol oxidation catalyst, converting cyclohexane to a combined yield of 32 percent of alcohol and ketone with a turnover number of 290 within two hours, a result that compared favorably with a copper-sodium silsesquioxane analog tested under the same conditions, and it oxidized the acetophenone precursor 1-phenylethanol with tert-butyl hydroperoxide in 90 percent yield and a turnover number of 900.

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Tetranuclear complexes obtained through the oxidative cleavage of a bis(phosphine) ligand, in this case 1,1-bis(diphenylphosphino)methane, were reported in 2019 as a palanquin-like Cu4Na4 cage in which the shortest distance between opposing silicon atoms of the silsesquioxane ligand measured 5.114 angstroms.8 This complex converted cyclohexane to cyclohexanol in 26 percent yield with a turnover number of 240 and an activation energy of 13.6 kilocalories per mole, and it oxidized 1-phenylethanol to acetophenone in essentially quantitative yield.

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Heterometallic Cu4/M4 architectures further diversified the structural landscape reported between 2019 and 2023. A series of eight cesium and rubidium templated Cu4M4 coordination polymers, in which the centers of neighboring cages were separated by 13.97 angstroms in the solid state, were developed for the hydrocarboxylation of cycloalkanes, converting cyclohexane to cyclohexanecarboxylic acid in up to 37.8 percent yield and cyclopentane to the corresponding acid in 26.4 percent yield, in addition to reaching a 45 percent yield in direct cyclohexane oxidation with hydrogen peroxide.9 A related cage-like Cu5Cs4 phenylsilsesquioxane, with cesium to cesium separations of 9.54 and 11.62 angstroms, was instead developed for the Baeyer-Villiger oxidation of cyclohexanone to epsilon-caprolactone with meta-chloroperoxybenzoic acid, reaching a quantitative yield and a turnover number of 250 under microwave irradiation, and it additionally supported a tandem route directly from cyclohexane to the lactone in 17 percent yield, together with alcohol oxidations reaching 90 percent yield in the conversion of 1-phenylethanol to acetophenone.10

\n

The record for nuclearity in this family has continued to rise, from a Cu12 cage decorated with additional Cu(I) phosphine moieties in 2024, whose copper-copper-copper trimer units are significantly distorted with angles of 140.70 and 141.77 degrees, to a Cu13Na2 cage assembled with the assistance of acetate ligands in 2025, the latter structure solved using synchrotron radiation.11,12 The Cu12 complex proved to be an active catalyst for both the peroxidative oxidation and the oxidative carboxylation of C2 to C4 alkanes, reaching a turnover number of up to 534 in propane oxidation and a 50 percent combined yield of pivalic and isovaleric acids in the carboxylation of isobutane, and it oxidized 1-phenylethanol to acetophenone in 96 percent yield with a turnover number of 960. The Cu13Na2 cage itself was tested as a precatalyst in the Baeyer-Villiger oxidation of cyclohexanone, reaching essentially quantitative yields of epsilon-caprolactone with meta-chloroperoxybenzoic acid as oxidant, and it also supported a direct tandem route from cyclohexane to the same lactone in 25 to 26 percent yield, a modest but meaningful improvement over the heptanuclear Cu7-benzoate congener from the same group on this more demanding substrate.12

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An octanuclear Cu8 complex bearing 3-phenyl-5-(2-pyridyl)pyrazolate ligands, in which two zigzag Cu4 tetramers are sandwiched by two cyclic pentameric silsesquioxane ligands with a longest intramolecular copper to copper separation of 11.08 angstroms, was likewise synthesized as an alkane oxidation catalyst, converting n-heptane to a 14 percent yield of oxidation products and methylcyclohexane to a 15 percent yield under comparable conditions with hydrogen peroxide and nitric acid as promoter.13

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\n
\n\"X-ray\n\"X-ray\n
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Figure 9. X-ray crystal structure of the record-nuclearity Cu13Na2 cage of Bilyachenko et al., Chem. Eur. J. 2025, 31, e202403604 (ref. 12), rendered directly from the deposited crystallographic coordinates. The left view shows the fused copper-siloxanolate core, with the crystallographically independent Cu1 and Cu2 centers and their symmetry-related counterparts (Cu3, Cu4 and primed equivalents) bridged by phenylsiloxanolate oxygens. The right view, rotated to look down the pseudo-macrocyclic axis, shows how the copper centers are threaded through the large siloxanolate ring formed by the ligand framework. Acetate ligands and the two bridging sodium centers that complete the Cu13Na2 formulation lie above and below this copper-rich core and are omitted here for clarity.

\n
\n

What Crystallography Reveals: Emerging Structural Trends

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Several patterns recur across this body of crystallographic work regardless of which metal is involved. The alkali metal cation present during self-assembly, whether lithium, sodium, potassium, rubidium, or cesium, is rarely a passive spectator. Its ionic radius consistently governs whether the silsesquioxane ligand adopts a cyclic or acyclic conformation and whether the resulting cage is neutral, cationic, or anionic, a relationship documented independently for copper, manganese, and iron systems. A second recurring theme is the steady increase in reported nuclearity over time within the copper family in particular, from the two-copper cooling tower of 2013 to cages containing twelve or thirteen copper centers within the past two years, a trend that appears to reflect refinements in self-assembly conditions and the increasing use of synchrotron radiation to solve structures that would otherwise diffract poorly. Finally, the correlation between confirmed cage topology and function, whether catalytic activity in oxidation chemistry, single-molecule magnet behavior, or luminescence thermometry, illustrates why single-crystal X-ray diffraction remains indispensable in this field rather than a merely confirmatory afterthought. Spectroscopic and computational methods can propose a plausible structure, but only diffraction data have consistently distinguished between the closely related cage topologies that give rise to markedly different physical and chemical properties.

\n

Conclusions and Outlook

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The metal-POSS complexes surveyed here span nearly the entire periodic table, from copper cages of steadily increasing nuclearity to the first actinide example reported only in 2024, and in every case single-crystal X-ray diffraction has been the method that transformed a plausible formula into a confirmed molecular structure. The copper family in particular continues to grow at a pace that suggests further records in nuclearity are likely within the next few years, while the lanthanide and actinide subfields remain comparatively open for structural discovery. For a research program centered on zinc Schiff base and imine-functionalized POSS chemistry, the comparative view offered by this survey suggests that the alkali metal template effect documented so thoroughly for copper, manganese, and iron systems may offer an underexplored strategy for directing the nuclearity and topology of future zinc-based cages as well.

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\n

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\n
","doi":"https://doi.org/10.59350/8e62f-05m22","guid":"tag:blogger.com,1999:blog-2875892712213933214.post-7230213059130383354","image":"https://blogger.googleusercontent.com/img/a/AVvXsEgbtkRdpRYiO2JHyQ1SnSxcpdDJhpJDd_a5auAqpTWOOL0NnM45ib0cA18ej-HckPJmc315dogMruGHs6Ao2P27QWrzlbAkY5GiffVrXTuWoGxtbeNEcUKo8iqDnMma_icTxMgnDrDNbFLere6HAUbZkyhjgiAzEHxnUvOffUijinsjhoJHsgPhsM0MbhE=s72-c","language":"en","license":"https://creativecommons.org/licenses/by/4.0/legalcode","published_at":1788998400,"reference":[{"id":"https://doi.org/10.1016/0277-5387(95)85009-0","unstructured":"Feher, F. J., & Budzichowski, T. A. (1995). Silasesquioxanes as ligands in inorganic and organometallic chemistry. Polyhedron, 14(22), 3239\u20133253."},{"id":"https://doi.org/10.1002/ejic.201300878","unstructured":"Bilyachenko, A. N., Dronova, M. S., Yalymov, A. I., Korlyukov, A. A., Shul'pina, L. S., Arkhipov, D. E., Shubina, E. S., Levitsky, M. M., Kirilin, A. D., & Shul'pin, G. B. (2013). Binuclear Cage\u2010Like Copper(II) Silsesquioxane (\"Cooling Tower\") \u2013 Its High Catalytic Activity in the Oxidation of Benzene and Alcohols. European Journal of Inorganic Chemistry, 2013(30), 5240\u20135246."},{"id":"https://doi.org/10.1021/acs.inorgchem.7b00061","unstructured":"Bilyachenko, A. N., Kulakova, A. N., Levitsky, M. M., Petrov, A. A., Korlyukov, A. A., Shul'pina, L. S., Khrustalev, V. N., Dorovatovskii, P. V., Vologzhanina, A. V., Tsareva, U. S., Golub, I. E., Gulyaeva, E. S., Shubina, E. S., & Shul'pin, G. B. (2017). Unusual Tri-, Hexa-, and Nonanuclear Cu(II) Cage Methylsilsesquioxanes: Synthesis, Structures, and Catalytic Activity in Oxidations with Peroxides. Inorganic Chemistry, 56(7), 4093\u20134103."},{"id":"https://doi.org/10.1021/acs.inorgchem.8b01496","unstructured":"Astakhov, G. S., Bilyachenko, A. N., Korlyukov, A. A., Levitsky, M. M., Shul'pina, L. S., Bantreil, X., Lamaty, F., Vologzhanina, A. V., Shubina, E. S., Dorovatovskii, P. V., Nesterov, D. 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M., & Shul'pin, G. B. (2023). Cagelike Rb2-, K2-, and Na2-Tetracopper(II) Silsesquioxanes with Quaternary Ammonium Cations: Synthesis, Structures, and Catalytic Activity. Organometallics, 42(18), 2577\u20132589."},{"id":"https://doi.org/10.3390/molecules27238505","unstructured":"Bilyachenko, A. N., Khrustalev, V. N., Gutsul, E. I., Zueva, A. Y., Korlyukov, A. A., Shul'pina, L. S., Ikonnikov, N. S., Dorovatovskii, P. V., Gelman, D., Shubina, E. S., & Shul'pin, G. B. (2022). Hybrid Silsesquioxane/Benzoate Cu7-Complexes: Synthesis, Unique Cage Structure, and Catalytic Activity. Molecules, 27(23), 8505."},{"id":"https://doi.org/10.3390/catal9020154","unstructured":"Kulakova, A. N., Khrustalev, V. N., Zubavichus, Y. V., Shul'pina, L. S., Shubina, E. S., Levitsky, M. M., Ikonnikov, N. S., Bilyachenko, A. N., Kozlov, Y. N., & Shul'pin, G. B. (2019). Palanquin-Like Cu4Na4 Silsesquioxane Synthesis (via Oxidation of 1,1-bis(Diphenylphosphino)methane), Structure and Catalytic Activity in Alkane or Alcohol Oxidation with Peroxides. Catalysts, 9(2), 154."},{"id":"https://doi.org/10.1021/acs.cgd.1c01225","unstructured":"Bilyachenko, A. N., Astakhov, G. S., Kulakova, A. N., Korlyukov, A. A., Zubavichus, Y. V., Dorovatovskii, P. V., Shul'pina, L. S., Shubina, E. S., Ikonnikov, N. S., Kirillova, M. V., Zueva, A. Y., Kirillov, A. M., & Shul'pin, G. B. (2022). Exploring Cagelike Silsesquioxane Building Blocks for the Design of Heterometallic Cu4/M4Architectures. Crystal Growth & Design, 22(4), 2146\u20132157."},{"id":"https://doi.org/10.1021/acs.inorgchem.3c01989","unstructured":"Bilyachenko, A. N., Arteev, I. S., Khrustalev, V. N., Shul'pina, L. S., Korlyukov, A. A., Ikonnikov, N. S., Shubina, E. S., Kozlov, Y. N., Reis Concei\u00e7\u00e3o, N., Guedes da Silva, M. F. C., Mahmudov, K. T., & Pombeiro, A. J. L. (2023). Cage-like Cu5Cs4-Phenylsilsesquioxanes: Synthesis, Supramolecular Structures, and Catalytic Activity. Inorganic Chemistry, 62(33), 13573\u201313586."},{"id":"https://doi.org/10.1021/acs.inorgchem.4c02806","unstructured":"Bilyachenko, A. N., Khrustalev, V. N., Arteev, I. S., Shul'pina, L. S., Ikonnikov, N. S., Kirillova, M. V., Shubina, E. S., Kirillov, A. M., Kozlov, Y. N., Lobanov, N. N., Ragimov, K. G., & Sun, D. (2024). Cu12-Methylsilsesquioxane Cage Decorated with Cu(dppe)2 Moieties for Mild Oxidative Functionalization of Alkanes. Inorganic Chemistry, 63(43), 20404\u201320414."},{"id":"https://doi.org/10.1002/chem.202403604","unstructured":"Bilyachenko, A. N., Khrustalev, V. N., Huang, Z., Dorovatovskii, P. V., Shubina, E. S., Lobanov, N. N., Wang, Z., Ragimov, K., Reis Concei\u00e7\u00e3o, N., Mahmoud, A. G., & Pombeiro, A. J. L. (2024). Combination of Phenylsilsesquioxane and Acetate Ligands as an Approach to a Record High Nuclear Cu13Na2\u2010Cage. Synthesis, Unique Structure, and Catalytic Activity. Chemistry \u2013 A European Journal, 31(5)."},{"id":"https://doi.org/10.1039/d4dt02690j","unstructured":"Bilyachenko, A. N., Khrustalev, V. N., Huang, Z., Shul'pina, L. S., Dorovatovskii, P. V., Shubina, E. S., Ikonnikov, N. S., Lobanov, N. N., Ragimov, K., & Sun, D. (2024). An octanuclear 3-phenyl-5-(2-pyridyl)pyrazolate/phenylsilsesquioxane complex: synthesis, unique structure, and catalytic activity. Dalton Transactions, 53(48), 19102\u201319106."},{"id":"https://doi.org/10.3390/molecules21050665","unstructured":"Bilyachenko, A., Yalymov, A., Shul'pina, L., Mandelli, D., Korlyukov, A., Vologzhanina, A., Es'kova, M., Shubina, E., Levitsky, M., & Shul'pin, G. (2016). Novel Cage-Like Hexanuclear Nickel(II) Silsesquioxane. Synthesis, Structure, and Catalytic Activity in Oxidations with Peroxides. Molecules, 21(5), 665."},{"id":"https://doi.org/10.1002/zaac.200800292","unstructured":"Lorenz, V., Blaurock, S., & Edelmann, F. T. (2008). The First Heterobimetallic Metallasilsesquioxane Derivatives of Manganese. Zeitschrift F\u00fcr Anorganische Und Allgemeine Chemie, 634(15), 2819\u20132824."},{"id":"https://doi.org/10.1039/d2qi01054b","unstructured":"Astakhov, G. S., Khrustalev, V. N., Dronova, M. S., Gutsul, E. I., Korlyukov, A. A., Gelman, D., Zubavichus, Y. V., Novichkov, D. A., Trigub, A. L., Shubina, E. S., & Bilyachenko, A. N. (2022). Cage-like manganesesilsesquioxanes: features of their synthesis, unique structure, and catalytic activity in oxidative amidations. Inorganic Chemistry Frontiers, 9(17), 4525\u20134537."},{"id":"https://doi.org/10.1021/acs.inorgchem.3c02040","unstructured":"Bilyachenko, A. N., Gutsul, E. I., Khrustalev, V. N., Chusova, O., Dorovatovskii, P. V., Aliyeva, V. A., Paninho, A. B., Nunes, A. V. M., Mahmudov, K. T., Shubina, E. S., & Pombeiro, A. J. L. (2023). A Family of Cagelike Mn-Silsesquioxane/Bathophenanthroline Complexes: Synthesis, Structure, and Catalytic and Antifungal Activity. Inorganic Chemistry, 62(38), 15537\u201315549."},{"id":"https://doi.org/10.1021/acs.inorgchem.3c03587","unstructured":"Bilyachenko, A. N., Khrustalev, V. N., Dorovatovskii, P. V., Shul'pina, L. S., Ikonnikov, N. S., Shubina, E. S., Lobanov, N. N., Aliyeva, V. A., Nunes, A. V. M., Mahmudov, K. T., Kozlov, Y. N., & Pombeiro, A. J. L. (2024). Fe(III)-Based Phenylsilsesquioxane/Acetylacetonate Complexes: Synthesis, Cage-like Structure, and High Catalytic Activity. Inorganic Chemistry, 63(4), 1909\u20131918."},{"id":"https://doi.org/10.1021/acs.inorgchem.4c01748","unstructured":"Shen, Q., Sheng, K., Gao, Z.-Y., Bilyachenko, A., Huang, X.-Q., Azam, M., Tung, C.-H., & Sun, D. (2024). Vanadium-Silsesquioxane Nanocages as Heterogeneous Catalysts for Synthesis of Quinazolinones. Inorganic Chemistry, 63(28), 13022\u201313030."},{"id":"https://doi.org/10.1021/ic101809r","unstructured":"Di Iulio, C., Jones, M. D., Mahon, M. F., & Apperley, D. C. (2010). Zinc(II) Silsesquioxane Complexes and Their Application for the Ring-Opening Polymerization of rac-Lactide. Inorganic Chemistry, 49(22), 10232\u201310234."},{"id":"https://doi.org/10.1002/chem.202002996","unstructured":"Janeta, M., Lis, T., & Szafert, S. (2020). Zinc Imine Polyhedral Oligomeric Silsesquioxane as a Quattro\u2010Site Catalyst for the Synthesis of Cyclic Carbonates from Epoxides and Low\u2010Pressure CO2. Chemistry \u2013 A European Journal, 26(60), 13686\u201313697."},{"id":"https://doi.org/10.1002/1521-3773(20010401)40:7%3c1279::aid-anie1279%3e3.0.co;2-2","unstructured":"Gun'ko, Y. K., Reilly, R., Edelmann, F. T., & Schmidt, H.-G. (2001). The First CeIV Metallasilsesquioxane Complex: [Ce{(c-C6H11)8Si8O13}2(py)3]. Angewandte Chemie International Edition, 40(7), 1279\u20131281. https://doi.org/10.1002/1521-3773(20010401)40:7%3c1279::aid-anie1279%3e3.0.co;2-2"},{"id":"https://doi.org/10.1002/ejic.201000186","unstructured":"Lorenz, V., Blaurock, S., Hrib, C. G., & Edelmann, F. T. (2010). Coupling of Silsesquioxane Cages in the Coordination Sphere of Erbium. European Journal of Inorganic Chemistry, 2010(18), 2605\u20132608."},{"id":"https://doi.org/10.1002/chem.202003351","unstructured":"Kulakova, A. N., Bilyachenko, A. N., Levitsky, M. M., Khrustalev, V. N., Shubina, E. S., Felix, G., Mamontova, E., Long, J., Guari, Y., & Larionova, J. (2020). New Luminescent Tetranuclear Lanthanide\u2010Based Silsesquioxane Cage\u2010Like Architectures. Chemistry \u2013 A European Journal, 26(70), 16594\u201316598."},{"id":"https://doi.org/10.1002/ejic.202100308","unstructured":"Kulakova, A. N., Nigoghossian, K., F\u00e9lix, G., Khrustalev, V. N., Shubina, E. S., Long, J., Guari, Y., Carlos, L. D., Bilyachenko, A. N., & Larionova, J. (2021). New Magnetic and Luminescent Dy(III) and Dy(III)/Y(III) Based Tetranuclear Silsesquioxane Cages. European Journal of Inorganic Chemistry, 2021(27), 2696\u20132701."},{"id":"https://doi.org/10.1039/d3ra04901a","unstructured":"F\u00e9lix, G., Sene, S., Kulakova, A., Bilyachenko, A. N., Khrustalev, V. N., Shubina, E. S., Guari, Y., & Larionova, J. (2023). Tetranuclear lanthanide-based silsesquioxanes: towards a combination of a slow relaxation of the magnetization and a luminescent thermometry. RSC Advances, 13(37), 26302\u201326312."},{"id":"https://doi.org/10.1016/j.chphma.2022.04.008","unstructured":"Sheng, K., Wang, R., Bilyachenko, A., Khrustalev, V., Jagodi\u010d, M., Jagli\u010di\u0107, Z., Li, Z., Wang, L., Tung, C., & Sun, D. (2022). Tridecanuclear Gd(III)-silsesquioxane: Synthesis, structure, and magnetic property. ChemPhysMater, 1(4), 247\u2013251."},{"id":"https://doi.org/10.1039/d3cc05390c","unstructured":"Tricoire, M., Jori, N., Fadaei Tirani, F., Scopelliti, R., Z\u0306ivkovi\u0107, I., Natrajan, L. S., & Mazzanti, M. (2024). A trinuclear metallasilsesquioxane of uranium(iii). Chemical Communications, 60(1), 55\u201358."},{"id":"https://doi.org/10.1039/b407471h","unstructured":"Duchateau, R., Dijkstra, T. W., Severn, J. R., van Santen, R. A., & Korobkov, I. V. (2004). Synthesis and characterization of tin containing polyhedral oligometallasilsesquioxanes (POMSS). Dalton Transactions, (17), 2677."},{"id":"https://doi.org/10.1002/zaac.200700370","unstructured":"Lorenz, V., Blaurock, S., & Edelmann, F. T. (2008). [{\u03bc\u2010Cy8Si8O13}2Ca(DME)Ca(THF)2] \u2013 The First Metallasilsesquioxane Derivative of a Heavier Alkaline Earth Metal. Zeitschrift F\u00fcr Anorganische Und Allgemeine Chemie, 634(3), 441\u2013444."}],"rid":"cgwz4-t1w67","summary":"Polyhedral oligomeric silsesquioxanes (POSS) have long served as more than a hybrid organic-inorganic filler for polymers. Their partially condensed silanol forms present a rigid, oxygen-rich pocket that closely resembles a fragment of amorphous silica, and this pocket is an excellent ligand for metal ions of nearly every part of the periodic table.","tags":["Catalysis","Metal-POSS Complexes","POSS","Silsesquioxane","X-ray Crystallography"],"title":"Crystallographically Confirmed Metal-POSS Complexes","updated_at":1789111820,"url":"https://silsesquioxane.blogspot.com/2026/09/crystallographically-confirmed-metal.html","version":"v1"}},{"document":{"authors":[{"contributor_roles":[],"name":"The WiNoDa-Team"}],"blog":{"authors":null,"community_id":"d21c5e78-88bc-432c-a20b-4e8a8ead1693","created":1752796800,"current_feed_url":null,"description":"Wissenslabor f\u00fcr naturwissenschaftliche Sammlungen und objektzentrierte Daten","doi":"https://doi.org/10.59350/winoda","favicon":"https://rogue-scholar.org/api/communities/d21c5e78-88bc-432c-a20b-4e8a8ead1693/logo","feed_format":"application/atom+xml","feed_url":"https://winoda.de/feed/atom/","filter":null,"generator":"WordPress","home_page_url":"https://winoda.de","issn":null,"language":"deu","license":"https://creativecommons.org/licenses/by/4.0/legalcode","prefix":"10.59350","relative_url":null,"secure":true,"slug":"winoda","status":"active","subfield":"1209","title":"WiNoDa Knowledge Lab","updated":1789036758,"use_api":false},"blog_name":"WiNoDa Knowledge Lab","blog_slug":"winoda","content_html":"
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Die r\u00e4umliche Anordnung von Proben innerhalb einer Fundstelle kann Muster aufzeigen und Pflanzenreste mit fr\u00fcheren sozialen Praktiken in Verbindung bringen \"\ud83c\udf31\"

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\"Social
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Neugierig, wie das funktioniert? Finden Sie es am 9. Oktober in unserem geostatistischen \"Bring-Your-Data\"-Workshop mit dem Titel \"Pflanzenreste, r\u00e4umliche Erkenntnisse\" heraus, in dem Sie mehr \u00fcber folgende Themen erfahren:

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\"\ud83d\udd39\"R\u00e4umliche Struktur und Variabilit\u00e4t von Daten

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\"\ud83d\udd39\"Experimentelle Variogramme

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\"\ud83d\udd39\"Geostatistische Modelle

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\"\ud83d\udd39\"Durch Kriging erzeugte Vorhersagefl\u00e4chen

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\"\ud83d\udd39\"Arch\u00e4ologische Interpretation r\u00e4umlicher Muster

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Au\u00dferdem haben Sie die M\u00f6glichkeit, Ihre eigenen Daten zum Workshop mitzubringen und Unterst\u00fctzung bei der Aufbereitung f\u00fcr die geplanten Analysen zu erhalten \"\ud83d\udcbb\"

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Egal, ob Sie sich bereits mit Geostatistik auskennen oder einfach nur Lust haben, etwas Neues zu lernen \u2013 Sie sind herzlich eingeladen, dabei zu sein!

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Anmeldungen sind bis zum 25. September 2026 m\u00f6glich.

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Weitere Informationen und Anmeldung auf unserer Website: https://winoda.de/event/byod-de/
","doi":"https://doi.org/10.59350/v3gs5-x9f45","guid":"https://winoda.de/?p=15478","image":"https://winoda.de/wp-content/uploads/2026/08/BYOD.png","language":"de","license":"https://creativecommons.org/licenses/by/4.0/legalcode","published_at":1788998400,"rid":"7kaf8-7f655","summary":"Die r\u00e4umliche Anordnung von Proben innerhalb einer Fundstelle kann Muster aufzeigen und Pflanzenreste mit fr\u00fcheren sozialen Praktiken in Verbindung bringen \ud83c\udf31 Neugierig, wie das funktioniert?","tags":["WiNoDa Knowledge Lab Journal","BYOD","CfP","Datenkompetenz","Tools"],"title":"Call for Participants: Plant Remains, Spatial Gains. Bring-your-data geo-statistical workshop","updated_at":1789111812,"url":"https://winoda.de/2026/09/10/call-for-participants-plant-remains-spatial-gains-bring-your-data-geo-statistical-workshop/","version":"v1"}},{"document":{"authors":[{"affiliation":[{"id":"https://ror.org/051fd9666","name":"Case Western Reserve University"}],"contributor_roles":[],"family":"McGaugh","given":"Stacy","url":"https://orcid.org/0000-0002-9762-0980"}],"blog":{"authors":null,"community_id":"82262dc6-3666-40e2-939a-d4d637d0fd8f","created":1713312000,"current_feed_url":null,"description":"A Blog About the Science and Sociology of Cosmology and Dark Matter","doi":"https://doi.org/10.59350/tritonstation","favicon":"https://rogue-scholar.org/api/communities/82262dc6-3666-40e2-939a-d4d637d0fd8f/logo","feed_format":"application/atom+xml","feed_url":"https://tritonstation.com/feed/atom/","filter":null,"generator":"WordPress","home_page_url":"https://tritonstation.com","issn":null,"language":"eng","license":"https://creativecommons.org/licenses/by/4.0/legalcode","prefix":"10.59350","relative_url":null,"secure":true,"slug":"tritonstation","status":"active","subfield":"3103","title":"Triton Station","updated":1789075797,"use_api":true},"blog_name":"Triton Station","blog_slug":"tritonstation","content_html":"

I’ve been trying to think more seriously about the entity that set off the LZ experiment. I was dismissive of the possibility of it being dark matter, perhaps unfairly so. On further reflection, I feel only fairly dismissive.

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First, the formal significance that is claimed is 2.6\u03c3. That seems to be a fair and fairly conservative statement. So it seems something did happen, the question is what. The odds of a 2.6\u03c3 event are about 1 in 200, so a fluke seems unlikely.

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I can think of three generic possibilities:

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  1. It’s a fluke.
    2. \n\n\n\n
  2. It’s dark matter (huzzah!)
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  3. It’s some strange new particle-entity that is not dark matter.
    4. \n
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I remain of the opinion that the most likely possibility is that is is a fluke. I know I just said that seems unlikely, but “seems” is doing a lot of work here. I think it is fair to say that known explanations are excluded at this confidence, but that leaves a lot of unknowns. Most unknowns turn out to be boring.

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We’ve been down this road many times. The LHC has been running for many years now. It detected the Higgs particle, which was the last missing piece of the Standard Model. That’s a great success. It was hoped that the LHC would also reveal new physics beyond the Standard Model. That it has not done. But there have been many hints during its operation. These appear as glitches (deviations from expectation); there have been multiple glitches that appeared to be significant at the 2.something \u03c3 level. Each time such a glitch was reported, it resulted in a flurry of theoretical activity. Within days, the arxiv preprint server would be inundated with hundreds (literally hundreds) of preprints staking out a claim as to what the latest glitch might be. Each time more data were acquired, the glitch went away. So this seems like another such occasion, making (1), a fluke, seem like the least improbable outcome.

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This is why the [arbitrary] threshold for discovery is set at 5\u03c3 (1 in 3.5 million). Flukes at the 2.something \u03c3 level happen too easily, too often. This phenomenon is not restricted to particle physics. The same thing happens in astronomy all the time. All the gorram time. It’s almost as if nature places more probability in the tail of the distribution for “weird” events than the Gaussian statistics we use say there should be.

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Given this experience, finding a new particle outside the bounds of the Standard Model of Particle Physics seems a lot less likely than 1 in 200. Seems is again doing a lot of work here. How likely 1 in 200 hundred seems depends on your priors. If you’ve been working on this for a long time in the hopes of a positive result, these odds seem pretty good:

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\"I have been waiting for a positive result for, oh, my god, 40 years. So you can bet I'm very, very excited by the LZ results.\"

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Katy Freese

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If, like me, you’ve already convinced yourself that dark matter cannot explain the kinematic data for galaxies, then it is just another opportunity for the eyes to roll up inside the skull. Obviously we can’t both be right, which is why we do these experiments.

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So what about the other possibilities, (2) and (3)? If the event is real, it is tempting to believe that it is dark matter. That’s what the experiment was designed to detect, after all, so that’s a natural first assumption. But just because you’re looking for something doesn’t guarantee that when you find something you find what you’ve been looking for.

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As I’ve reviewed before, we’re way past the regime of what we expected to find. So it’d be great to find something, but there’s little reason at this point to expect that something to be what we set out to find. So it might be dark matter (2) or it might be something completely different (3). I’ve no way to weigh the odds of those possibilities because they both seem very unlikely.

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For WIMP-like dark matter we at least have some expectations, and this event does not conform to those expectations. It is too high energy. For every event like this one, the detector should have already recorded lots and lots of lower energy events.

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That doesn’t mean it isn’t dark matter (2), just that it isn’t what we expected. But we already missed out on what we were expecting, so maybe? Or maybe it is something unrelated (3), or nothing at all (1). One event does not help override whatever assumption bias we might have had about these possibilities to start.

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To be convincing…

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It occurs to me that I am likely to hold the putative detection of dark matter to a higher standard than other scientists. So what would I find convincing?

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I put the fifth criterion in parentheses because it is a very high bar, and I can conceive of being persuaded to soften it. It is also more advanced tuition than most physicists have contemplated, so let’s start with the more basic requirements.

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At present, none of the above criteria have been met by the new LZ result. There is an old claim to a significant detection by DAMA that satisfies the first criterion but was never independently reproduced, so fails the second criterion. Nobody outside the original experiment takes it seriously now for that reason. It is sobering to realize that while new and exciting, LZ has not yet progressed as far down this list as DAMA.

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Supposing both the first and second requirements are met, then we have a new particle. That is certainly interesting, but by itself would not mean we’ve found dark matter. When we’re in the realm of imagining new particles, there is a vast landscape of possibilities. Only some features in that landscape could qualify as dark matter; there are other possibilities that could exist but have nothing whatever to do with dark matter. So the properties of the particle have to be right, and there is a long list to satisfy.

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From a generic astronomical perspective, the fourth criterion is the most important. We have a pretty good idea of the mass density that dark matter needs to have in the solar neighborhood to explain Galactic kinematics. That’s what these experiments are trying to detect: the dark matter particles in our Galaxy’s dark matter halo that happen to be passing through just now. So for whatever we detect to qualify as the dark matter, there needs to be the right number of particles with the right mass to satisfy astronomical requirements.

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This fourth criterion is a pretty high bar. It does not suffice merely to find a new particle, it’s gotta be the right kind of particle and these particles have to exist with the right density. That can be measured, but it requires lots of detections: enough to work out the properties of the particles and how many are whizzing by. This is part of the disconnect I had in the last post with people complaining about statistical significance: they were focused on the significance of this one event; I was worried about having enough detections to estimate the mass density, or at least see if it is anywhere near the right ballpark. I’m more concerned with the astrophysical relevance of a new particle than with the new particle itself.

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This is a generic problem in the field of dark matter, being as it is at the interface of two different fields. Astronomers need dark matter; we don’t care so much what it is if it performs as required. Particle physicists heard we astronomers needed dark matter, so are more than happy to suggest possibilities, but are more interested in the particle itself than what it does for galaxies. I don’t say what it does for the universe because that’s a lower bar where any dynamically cold, non-baryonic mass will do. The cosmic density needs to be right, but there’s no way to measure the cosmic average, only the local density of the Galactic dark matter halo.

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The highest bar is the fifth criterion, which I think warrants its own post.

","doi":"https://doi.org/10.59350/3q11z-xt245","guid":"https://tritonstation.com/?p=13109","image":"https://tritonstation.com/wp-content/uploads/2026/09/nottheDMyourelookingofr.jpg","language":"en","license":"https://creativecommons.org/licenses/by/4.0/legalcode","published_at":1788998400,"rid":"0j7xh-d6340","summary":"I've been trying to think more seriously about the entity that set off the LZ experiment. I was dismissive of the possibility of it being dark matter, perhaps unfairly so. On further reflection, I feel only fairly dismissive.","tags":["Dark Matter","Particle Physics"],"title":"What can't it be?","updated_at":1789111809,"url":"https://tritonstation.com/2026/09/10/what-cant-it-be/","version":"v1"}},{"document":{"authors":[{"contributor_roles":[],"family":"Crueger","given":"Jens"}],"blog":{"authors":[{"name":"Redaktion iRights.info"}],"community_id":"7d3b25fd-a4a8-4155-8e76-99d6be06706a","created":1694736000,"current_feed_url":null,"description":"Urheberrecht und kreatives Schaffen in der digitalen Welt","doi":"https://doi.org/10.59350/irights","favicon":"https://rogue-scholar.org/api/communities/7d3b25fd-a4a8-4155-8e76-99d6be06706a/logo","feed_format":"application/atom+xml","feed_url":"https://irights.info/feed/atom","filter":null,"generator":"Other","home_page_url":"https://irights.info/","issn":null,"language":"deu","license":"https://creativecommons.org/licenses/by/4.0/legalcode","prefix":"10.59350","relative_url":null,"secure":true,"slug":"irights","status":"active","subfield":"3308","title":"iRights.info","updated":1789026321,"use_api":false},"blog_name":"iRights.info","blog_slug":"irights","content_html":"

In the media and on social media, there has been a growing number of concerned reports about AI companies that are buying up used books in large quantities and in a rather ominous manner. It is speculated that the large quantities of books acquired in this way are scanned, used for AI training, and irretrievably destroyed in the process. It is often suggested that copyright law is the reason why the books are being destroyed. Can this assumption be substantiated?
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The Destructive Scanning of Books

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The retro-digitization (usually referred to simply as \"digitization\") of books is typically carried out using scanning technology. Modern book scanners are capable of scanning books non-destructively. However, non-destructive scanning of books is a complex process, as irregularities caused by the book's binding must be compensated for during the scanning process.

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In contrast, in so-called destructive scanning, the book's binding is mechanically removed. This turns a book into a loose collection of pages that can be conveniently digitized using a sheet-fed scanner. Once the scanning process is complete, the book pages are then disposed of as waste paper.

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Why Antiquarian Bookstores Are Important for AI Training

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Digital data sources, such as web archives, have long been incorporated into the training of current AI models. The digitization of printed books is now the next stage in data acquisition. According to observers, tech companies are particularly focused on non-fiction books published between the 1970s and the 1990s.

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These books are likely to be of interest for three reasons: First, nonfiction books are valuable for AI training because of their content; they contain factual information that is still largely accurate and is integrated into linguistically sophisticated patterns of argumentation. Second, book titles published before the mid-1990s were generally released exclusively as print editions and have not been digitized since. Third, books from the period in question are still predominantly subject to copyright, which expires only 70 years after the author's death in both Germany and the U.S.

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Obtaining scans of these books from dubious third-party sources would be illegal. Therefore, from a copyright perspective, the purchased print editions of these books are particularly valuable to the companies.

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Technical Reasons for Destructive Scanning

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But why do AI companies accept the destruction of the books during the scanning process?

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First, technical aspects play a significant role in large-scale retro-digitization of books: As explained at the outset, destructive scanning is simpler, faster, and therefore more cost-effective. Although the AI industry appears economically strong, observers interpret the decision to use the most cost-effective digitization method as an indication of cost pressure in this \"highly competitive industry.\"

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Competitive considerations may also play a role, because while the books in question are not particularly old or unique, many of them are nevertheless rarely available on the antiquarian book market due to low print runs and scarcity. Whoever buys them first effectively removes them from the competition's reach, thereby gaining a small advantage for their AI model.

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Destructive Scanning Out of Concern for Copyright?

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A lawsuit between three plaintiff authors and the AI company Anthropic before the United States District Court for the Northern District of California (Bartz v. Anthropic) established a legal precedent regarding destructive book scanning in 2025.

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The central question here was whether destructive scanning, on the one hand, and the training of AI models using the content of acquired digitized books, on the other, fall under the so-called \"fair use principle.\"

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What is the fair use principle?
\nThe fair use principle is a legal doctrine found in some common law countries. It permits the use of copyrighted material for purposes of public education or intellectual production without requiring authorization for such use. Classic areas of application for fair use include commentary, criticism, parody, news reporting, research, and scholarship. Under German copyright law, instead of a general clause like fair use, there are narrow exceptions that permit certain uses (such as quotations, caricatures, parodies, educational and scholarly purposes, reporting on current events, etc.) regardless of the copyright holder's consent.
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The two central questions to be decided by the court must be considered separately:

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First, whether training AI models with the content of purchased digitized books is protected by the fair use doctrine.

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Second, whether destructive scanning constitutes a copyright-relevant copy of a work.

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According to Judge William Alsup, training AI models using the content of purchased digitized books was \"transformative in the truest sense of the word\" and therefore protected by the fair use doctrine. Destructive scanning should be classified as \"replacement scanning,\" in which a printed work is replaced by a digital work. This conversion of a purchased printed book into a digital book was classified by the court as a \"format change\" rather than a copy and is therefore also covered by fair use.

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A Landmark Ruling with Significant Implications

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The rule on format conversion\u2014also known as the \"format-shifting rationale\"\u2014thus promises, according to this landmark ruling, a certain degree of legal certainty for AI companies that destroy the books they have acquired for AI training through destructive scanning. The method that is more efficient from a technical standpoint is therefore also the more legally advisable one.

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However, it is a fallacy to assume that the court's ruling requires AI companies to destroy the digitized books. The lawsuit merely examined the specific digitization process as applied by Anthropic as part of \"Project Panama\"\u2014and classified it as fair use.

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E-books Instead of Print Books?

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If e-books were used for training instead of their printed counterparts, the time-consuming step of scanning\u2014and the associated issues of transportation, storage, and reuse\u2014would be eliminated.

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However, e-books can only become training data for AI models in two ways: the legal way\u2014that is, with the involvement of the rights holders of those e-books\u2014or by training with pirated copies. For AI companies, the legal route entails a significantly higher \"legal/practice/business slog\" (quote from Anthropic co-founder and CEO Dario Amodei).

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Training AI with pirated copies of e-books is not covered by fair use and thus constitutes a clear copyright infringement, Judge Alsup ruled.

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Fears of 'Fahrenheit 451' Scenarios

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Reports of AI companies purchasing large quantities of books from used bookstores have sparked, in some cases, fierce reactions in the media. The media discussion often references Ray Bradbury's novel *Fahrenheit 451*, a dystopia in which books are banned.

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A closer look at the relevant court ruling in this specific case reveals that there is no legal obligation to destroy retro-digitized books. Economic reasons for choosing the most cost-effective digitization method therefore appear to be the decisive factor when the AI industry employs destructive book scanning. Against the backdrop of the actions taken by major AI companies, calls for open-source AI models are currently growing louder, and with regard to the retro-digitization of books, there are also increasing calls for \"an open-source initiative or a similar nonprofit project.\"

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DOI for this text: \u00b7 Automatic DOI assignment for blogs via The Rogue Scholar

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The post Out of Concern for Copyright? AI Companies and Their Destructive Scanning of Books appeared first on iRights.info.

","doi":"https://doi.org/10.59350/ksfmn-23248","guid":"https://irights.info/?post_type=custom_artikel&p=32898","language":"en","license":"https://creativecommons.org/licenses/by/4.0/legalcode","published_at":1788998400,"rid":"bznwv-d6252","summary":"In the media and on social media, there has been a growing number of concerned reports about AI companies that are buying up used books in large quantities and in a rather ominous manner. It is speculated that the large quantities of books acquired in this way are scanned, used for AI training, and irretrievably [\u2026] The post Out of Concern for Copyright? AI Companies and Their Destructive Scanning of Books appeared first on iRights.info.","tags":["B\u00fccher","English","Generative KI","Urheberrecht","Urteile"],"title":"Out of Concern for Copyright? AI Companies and Their Destructive Scanning of Books","updated_at":1789111805,"url":"https://irights.info/artikel/out-of-concern-for-copyright-ai-companies-and-their-destructive-scanning-of-books/32898","version":"v1"}},{"document":{"authors":[{"contributor_roles":[],"family":"Roddie","given":"Rosaria"}],"blog":{"authors":null,"community_id":"d6ac84f0-4643-4ec0-bcd0-e21306f31948","created":1707091200,"current_feed_url":null,"description":null,"doi":"https://doi.org/10.59350/europepmc","favicon":"https://rogue-scholar.org/api/communities/d6ac84f0-4643-4ec0-bcd0-e21306f31948/logo","feed_format":"application/atom+xml","feed_url":"https://blog.europepmc.org/feed/atom","filter":null,"generator":"WordPress","home_page_url":"https://blog.europepmc.org","issn":null,"language":"eng","license":"https://creativecommons.org/licenses/by/4.0/legalcode","prefix":"10.59350","relative_url":null,"secure":true,"slug":"europepmc","status":"active","subfield":"1710","title":"Europe PMC News Blog","updated":1789039109,"use_api":true},"blog_name":"Europe PMC News Blog","blog_slug":"europepmc","content_html":"

The Medical Research Council and Europe PMC are developing an open UK Health Research Funding Portfolio Database and Interactive Dashboard to make data on health research funding from participating UK public bodies and medical research charities easier to find, compare, and reuse.

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Across the UK, public bodies and medical research charities support a vast range of health research. The most recent UK Health Research Analysis  gives a sense of the scale: it covered more than 23,500 awards from 173 funding organisations and over \u00a35 billion in health research spending in 2022. For two decades, UK Health Research Analyses have shown the value of bringing this information together. However, they have provided only periodic historical snapshots rather than a dynamic view of the changing funding landscape. A timely view is needed to answer questions: Who is funding what? Where is research taking place? How is investment changing over time?

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The Medical Research Council (MRC), part of UK Research and Innovation (UKRI), is working with Europe PMC, hosted by EMBL-EBI, to develop the UK Health Research Funding Portfolio Database and Interactive Dashboard. The project is in response to Action 11.1 of the UK Government’s Life Sciences Sector Plan, which calls for closer coordination across health and life sciences funders.

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Planned for release in March 2027, the tool will use the established health and research activity classifications and a user-friendly dashboard to bring more of the breadth and diversity of this investment into a coherent, regularly updated view. The public-facing dashboard will make it easier to explore award data from participating UK funders. For example, a funder could compare the number and value of awards across years, examine investment by health category and research activity, and identify potential overlap or complementary activity. Researchers and institutions could see which funders and recipient organisations are active in related areas and where work is taking place. Industry and investors could use the same view to understand UK research strengths, see how investment is changing across locations and research areas, and identify potential partnership opportunities. 

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Europe PMC has long supported open science by linking grants to publications and other research outputs, and by making grant data openly available through its Grant Finder and application programming interface (API). Its integration of Research Organization Registry (ROR) identifiers into Grant Finder shows how persistent identifiers can connect variations in institutional names and make grant searches more consistent. The project will build on Europe PMC’s well-established grant-data infrastructure. Existing Europe PMC grant data provides a strong foundation, while contributions from UK Governmental bodies and medical research charities\u2014including organisations outside the Europe PMC funder group\u2014will be essential to creating a representative national picture.

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A UK focus with wider benefits

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Although the data resulting from this project is UK-focussed for now, responding to a specific UK governmental policy commitment, the expanded data model remains applicable for Europe PMC's international funder group. GRIST, the longstanding infrastructure that supports Europe PMC funders in linking grants to research outputs, will be rebuilt as a modern, scalable, open-source infrastructure. Submission and correction workflows will be improved, alongside stronger validation and deduplication. The open GRIST API will expose the expanded data and, for Europe PMC funders, provide links from grants to publications and research data, helping users understand the outputs and wider impact of investment. Together, these changes are intended to improve data quality, reduce manual intervention over time and make grant data easier to maintain and reuse. Future growth of the tool could incorporate further datasets and categorisation.

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Why funder participation matters

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The value of the dashboard will depend on the quality and coverage of the data contributed to it. Participating funders will provide and update award records through agreed submission routes, while validation and correction processes will help ensure that investments are represented accurately and consistently. 

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We welcome interest from UK public bodies and medical research charities that fund health research. To learn more about participating, contact Rosa at roddie@ebi.ac.uk.

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Related links

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UK Health Research Analysis 2022\u00a0 |\u00a0 Life Sciences Sector Plan\u00a0 |\u00a0 Medical Research Council\u00a0 |\u00a0 Europe PMC\u00a0 |\u00a0 Europe PMC Grant Finder

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\u4e2d\u6587\u7248\u672c / Chinese version: POSS \u4e8c\u6c1f\u787c\u5149\u50ac\u5316\u5242:\u786b\u919a\u9009\u62e9\u6027\u6c27\u5316\u5236\u4e9a\u781c

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\"silsesquioxaneThe publication titled \"Polyhedral oligomeric silsesquioxane difluoroboron complexes as cooperative octo-site catalysts for the photooxidation of sulfides to sulfoxides\" by Mateusz Janeta and S\u0142awomir Szafert, published in Inorganic Chemistry Frontiers on April 17, 2025, presents a study on the development of novel metal-free photocatalysts. These catalysts are based on polyhedral oligomeric silsesquioxanes (POSS) functionalized with difluoroboron complexes.

\"Synthetic
Scheme 1. Synthesis of POSS-sal-BF2, POSS-tert-BF2, and POSS-npht-BF2. Isolated yields in parentheses.

Key Highlights

This research underscores the potential of POSS-based difluoroboron complexes as efficient, sustainable, and reusable photocatalysts for the selective oxidation of sulfides to sulfoxides, with implications for pharmaceutical synthesis and environmental applications.

Singlet Oxygen Quantum Yields

The singlet oxygen quantum yield (SOQY, \u03a6(1O2)) was determined by monitoring the photooxidation of DPA in methanol in the presence of the POSS derivatives. Changes in the DPA absorbance at 391 nm were measured over time using low concentrations of photosensitizer and DPA in order to minimize potential quenching of 1O2 by the photocatalyst. The SOQY values were calculated by plotting the change in DPA absorbance against irradiation time.

The calculated \u03a6(1O2) values for POSS-tert-BF2, POSS-sal-BF2, POSS-npht-BF2, prop-tert-BF2, prop-sal-BF2, and prop-npht-BF2 were 48%, 35%, 46%, 27%, 26%, and 18%, respectively, which highlights the high efficiency of POSS-tert-BF2 in generating singlet oxygen. A higher singlet oxygen quantum yield, and therefore a higher degree of DPA oxidation, was obtained for the octametallic POSS-tert-BF2, POSS-sal-BF2, and POSS-npht-BF2 than for the monometallic analogues prop-tert-BF2, prop-sal-BF2, and prop-npht-BF2 under the same reaction conditions. This can be attributed to the intramolecular cooperative effect in compounds bearing the POSS moiety, which was investigated further.

Photocatalytic Oxidation of Sulfides to Sulfoxides

Recent studies have demonstrated the powerful photocatalytic capabilities of POSS-tert-BF2, a boron difluoride-functionalized polyhedral oligomeric silsesquioxane. This system shows a significant singlet oxygen quantum yield and generates multiple reactive oxygen species, which makes it highly effective in oxidative transformations.

\"Photooxidation

Key findings from the study

The conversion of thioanisole was only 30% in pure DCM, whereas under the same reaction conditions in MeOH the conversion increased to 99%. Protic solvents such as MeOH and H2O are known to stabilize the intermediate involved in the formation of 1O2 and thereby to accelerate photooxidation. These differences in conversion also suggest that 1O2 can be identified as one of the reactive oxygen species involved in the photooxidation of thioanisole.

Comparing the activity of POSS compounds bearing various substituents on the phenyl ring, we observed that introducing steric hindrance, as in the tert-butyl groups at the 3- and 5-positions of the phenyl ring in POSS-tert-BF2, significantly increased the reaction efficiency, giving 99% conversion in 40 minutes compared with 70% for POSS-sal-BF2, which lacks bulky substituents. Introducing steric hindrance at the 5,6-positions of the phenyl ring in POSS-npht-BF2, by replacing the phenyl ring with a naphthalene ring, also improved the efficiency relative to POSS-sal-BF2, although it remained lower than that of POSS-tert-BF2. This underscores the critical role of steric hindrance at the 3-position of the phenyl ring in promoting the conversion of thioanisole. POSS-tert-BF2 therefore exhibits high efficiency in the photocatalytic oxidation of thioanisole and was studied in greater detail.

The reaction progress was monitored in real time by NMR spectroscopy, which revealed that the conversion of thioanisole to methyl phenyl sulfoxide with POSS-tert-BF2 as the photosensitizer increased steadily over time, reaching complete conversion within 40 minutes in accordance with zero-order kinetics. By comparison, the use of prop-tert-BF2 resulted in only 65% substrate conversion after 40 minutes, with full conversion achieved after 60 minutes. These findings clearly demonstrate the superior reaction efficiency and faster catalytic performance of POSS-tert-BF2 relative to prop-tert-BF2.

The higher conversion of thioanisole obtained with the octametallic POSS-tert-BF2 (99%) than with the monometallic analogue prop-tert-BF2 (65%) under the same reaction conditions supports the occurrence of intramolecular cooperative catalysis in POSS-tert-BF2. This observation is consistent with the enhancement recorded in the singlet oxygen quantum yields. A similar intramolecular cooperative effect was previously reported for Zn4@POSS-1, which contains the POSS-1 ligand, in the formation of cyclic carbonates from epoxides.37 A comparable enhancement in efficiency was observed for POSS-sal-BF2 and POSS-npht-BF2. Comparing the activity of POSS-npht-BF2 with that of prop-npht-BF2, a higher yield of 90% versus 60% was obtained for POSS-npht-BF2. The activity of POSS-sal-BF2 is likewise higher than that of prop-sal-BF2, at 70% versus 59%.

\"Proposed
Scheme 2. Proposed reaction mechanisms of sulfide-selective oxidation by POSS-tert-BF2 in the presence of O2.

Substrate Scope

To assess the versatility of POSS-tert-BF2 as a photocatalyst in the photooxidation of thioanisole derivatives in methanol, a series of substrates bearing various substituents was evaluated. Thioanisole derivatives containing the electron-donating group \u2013CH3 and the electron-withdrawing groups \u2013CN, \u2013CHO, and \u2013C(O)CH3 achieved high yields of 99%, 82%, 78%, and 96%, respectively. Bromine-substituted derivatives at the ortho and meta positions also gave high yields of 99%.

\"Substrate

These results highlight the potential of POSS-based systems in green and efficient photocatalytic oxidation chemistry.

Full CitationMateusz Janeta and S\u0142awomir Szafert. \"Polyhedral oligomeric silsesquioxane difluoroboron complexes as cooperative octo-site catalysts for the photooxidation of sulfides to sulfoxides.\" Inorganic Chemistry Frontiers, 2025, 12, 4666-4676.
DOI: 10.1039/D5QI00323G
Full text: Inorganic Chemistry Frontiers \u2192 RSC Publishing
\"Research
","doi":"https://doi.org/10.59350/pznaw-y5e39","guid":"tag:blogger.com,1999:blog-2875892712213933214.post-4039579808081725822","image":"https://blogger.googleusercontent.com/img/b/R29vZ2xl/AVvXsEieZxQDVRgNeI8fmnmqP8Q-yYBJlE79nqTichFmo5SytMhZfFD9URo5d6StOfaKM95COqeqIfh2B72C6LWys5dyJBBhR_9TiY3UJG08-bqRwv6I6yfBgCvyAfYfQ3BvBcaZ5gedOnqAAkaqMwyhpv_luxChyTOmfKo_RZwCcEmXc_iEntpFdRVVGSMD-6g/s72-w99-h91-c/Research%20Highlights%20-%20Copy.png","language":"en","license":"https://creativecommons.org/licenses/by/4.0/legalcode","published_at":1788998400,"rid":"8jtxv-rdg17","summary":"\u4e2d\u6587\u7248\u672c / Chinese version: POSS \u4e8c\u6c1f\u787c\u5149\u50ac\u5316\u5242:\u786b\u919a\u9009\u62e9\u6027\u6c27\u5316\u5236\u4e9a\u781c The publication titled \"Polyhedral oligomeric silsesquioxane difluoroboron complexes as cooperative octo-site catalysts for the photooxidation of sulfides to sulfoxides\" by Mateusz Janeta and S\u0142awomir Szafert, published in Inorganic Chemistry Frontiers on April 17, 2025, presents a study on the development of novel metal-free photocatalysts.","tags":["Catalysis","Imine-POSS","Photochemistry","POSS","POSS Functionalization"],"title":"POSS Difluoroboron Photocatalysts for Sulfide Oxidation","updated_at":1789025423,"url":"https://silsesquioxane.blogspot.com/2026/09/poss-difluoroboron-photocatalysts-for.html","version":"v1"}},{"document":{"authors":[{"affiliation":[{"name":"Bielefeld University, Medical Faculty"}],"contributor_roles":[],"family":"Friederichs","given":"Hendrik","url":"https://orcid.org/0000-0001-9671-5235"}],"blog":{"authors":null,"community_id":"304adf51-cbb7-4ff1-a505-1dc06082fbad","created":1776988800,"current_feed_url":null,"description":"Aktuelle Einblicke aus der medizinischen Bildungsforschung \u2014 evidenzbasiert, verst\u00e4ndlich, mit gelegentlichem Augenzwinkern.","doi":"https://doi.org/10.59350/medical_education","favicon":"https://rogue-scholar.org/api/communities/304adf51-cbb7-4ff1-a505-1dc06082fbad/logo","feed_format":"application/rss+xml","feed_url":"https://medical-education.pages.ub.uni-bielefeld.de/research/mes-blog/blog.xml","filter":null,"generator":"Quarto","home_page_url":"https://medical-education.pages.ub.uni-bielefeld.de/research/mes-blog/blog.html","issn":null,"language":"eng","license":"https://creativecommons.org/licenses/by/4.0/legalcode","prefix":"10.59350","relative_url":null,"secure":true,"slug":"medical_education","status":"active","subfield":"2739","title":"Entscheiden(d) lernen","updated":1788991200,"use_api":null},"blog_name":"Entscheiden(d) lernen","blog_slug":"medical_education","content_html":"

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Im Oktober beginnen viele junge Menschen ihr Medizinstudium. Viele von ihnen werden in den ersten Wochen denselben Gedanken haben, n\u00e4mlich dass alle anderen im H\u00f6rsaal besser vorbereitet, kl\u00fcger und sicherer wirken als sie selbst. Dieser Gedanke hat einen Namen, er ist gut untersucht, und er ist erstaunlich verbreitet.

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Der Gedanke in der ersten Woche

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Die allererste Vorlesung. Um Euch herum sitzen Leute, die sich offenbar m\u00fchelos Fachbegriffe merken, die im Seminar als Erste die Hand heben und die schon wissen, wo die Bibliothek ist. Ihr selbst habt das Gef\u00fchl, durch einen Zufall hier gelandet zu sein. Die Zulassung war Gl\u00fcck, der gute Abiturschnitt eine Verkettung g\u00fcnstiger Umst\u00e4nde, und irgendwann wird jemand merken, dass Ihr eigentlich gar nicht hierhergeh\u00f6rt.

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Wenn Euch das bekannt vorkommt, seid Ihr in gro\u00dfer Gesellschaft. Zwei Metaanalysen aus diesem Jahr kommen unabh\u00e4ngig voneinander zu dem Ergebnis, dass etwa die H\u00e4lfte aller Medizinstudierenden weltweit ausgepr\u00e4gte Impostor-Gef\u00fchle berichtet [1, 2]. Zum Studienstart liegt der Anteil noch deutlich h\u00f6her. In einer L\u00e4ngsschnittstudie mit 257 Erstsemestern hatten fast neun von zehn schon in den ersten Wochen hohe Werte, und bis zum Jahresende stiegen sie weiter [3].

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Was das Impostor-Ph\u00e4nomen ist

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Beschrieben haben es die Psychologinnen Pauline Clance und Suzanne Imes 1978 bei mehr als 150 beruflich sehr erfolgreichen Frauen. Ihre Klientinnen waren \u00fcberzeugt, ihre Erfolge nicht verdient zu haben, und lebten in der Erwartung, irgendwann als Betr\u00fcgerinnen entlarvt zu werden [4]. Das T\u00fcckische daran ist ein Kreislauf. Wer vor einer Pr\u00fcfung \u00fcberm\u00e4\u00dfig viel lernt und besteht, schreibt das dem Flei\u00df zu, nicht der eigenen F\u00e4higkeit. Wer aufgeschoben hat und trotzdem durchkommt, schreibt es dem Gl\u00fcck zu. In beiden F\u00e4llen bleibt die eigene Kompetenz unsichtbar, und die n\u00e4chste Pr\u00fcfung beginnt mit denselben Zweifeln.

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Zwei Dinge sind dabei wichtig. Das Impostor-Ph\u00e4nomen ist keine Krankheit und keine Diagnose, es steht in keinem Klassifikationssystem. Und der verbreitete Begriff \"Impostor-Syndrom\" f\u00fchrt in die Irre, weil er nahelegt, das Problem s\u00e4\u00dfe in der Person. Eine Forschungsgruppe hat 2020 daf\u00fcr pl\u00e4diert, das Ph\u00e4nomen konsequent im Kontext zu betrachten, also in den Umgebungen, die solche Gef\u00fchle hervorrufen [5]. Genau darum geht es im n\u00e4chsten Abschnitt.

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Warum ausgerechnet das Medizinstudium

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Die Antwort beginnt mit der Auswahl. Wer einen Medizinstudienplatz bekommt, geh\u00f6rte an der Schule zu den Besten. Im H\u00f6rsaal sitzen dann 300 Menschen, auf die das gleiche zutrifft, und die vertraute Referenzgruppe ist \u00fcber Nacht verschwunden. Wer sich bisher am oberen Rand verortet hat, findet sich pl\u00f6tzlich in der Mitte wieder, ohne dass sich an den eigenen F\u00e4higkeiten etwas ge\u00e4ndert h\u00e4tte.

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Dazu kommt eine Kultur, die Perfektion als Normalzustand behandelt. Ein \u00dcberblick \u00fcber die Literatur beschreibt, wie das Medizinstudium hohe Anspr\u00fcche und Selbstkritik nicht nur anzieht, sondern aktiv trainiert [6]. Eine britische Studie fand, dass die Impostor-Werte umso h\u00f6her lagen, je weiter unten jemand im Pr\u00fcfungsranking stand [7]. Das klingt zun\u00e4chst naheliegend, hat aber eine Pointe. In einer Gruppe, in der alle zu den Besten ihres Jahrgangs geh\u00f6rten, muss ein Ranking trotzdem die H\u00e4lfte in die untere H\u00e4lfte sortieren. Es verteilt also Zweifel an Menschen, deren Leistung sich gar nicht verschlechtert hat.

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Ein dritter Faktor ist die Frage, ob man sich zugeh\u00f6rig f\u00fchlt. Kanadische Studierende, die im Studium erlebten, dass sie etwas k\u00f6nnen und dass sie aus eigenem Antrieb lernen, berichteten deutlich weniger Impostor-Gef\u00fchle. Wer sich dagegen vor allem von au\u00dfen getrieben f\u00fchlte, von Noten, Erwartungen und Vergleich, berichtete mehr davon [8]. Und wer an seiner Fakult\u00e4t zu einer Minderheit geh\u00f6rt, ist besonders betroffen. In den USA berichteten Studierende aus unterrepr\u00e4sentierten Gruppen an \u00fcberwiegend wei\u00dfen Fakult\u00e4ten fast dreimal so h\u00e4ufig starke Impostor-Gef\u00fchle wie an Hochschulen mit \u00fcberwiegend schwarzer Studierendenschaft [9].

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Das Impostor-Gef\u00fchl ist also weniger eine Eigenschaft, die man mitbringt, als eine Reaktion auf eine Situation. Das erkl\u00e4rt, warum es in \u00dcbergangsphasen am st\u00e4rksten ist, nach dem Studienstart, beim Eintritt in die Klinik, zu Beginn der Weiterbildung. So z. B. hatten britische Chirurg*innen in Weiterbildung deutlich h\u00f6here Werte als ihre fertig ausgebildeten Kolleg*innen [10]. Es wird besser, aber nicht von allein und nicht schnell.

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Warum es nicht egal ist

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Man k\u00f6nnte einwenden, ein bisschen Selbstzweifel schadet nicht. Ein bisschen stimmt das auch. Problematisch wird es, wenn die Zweifel anhalten. Bei \u00c4rzt*innen in Weiterbildung war ein ausgepr\u00e4gtes Impostor-Erleben ein eigenst\u00e4ndiger Risikofaktor f\u00fcr Angstsymptome und Burnout [11], und bei einer Studie an mehr als 3.000 US-\u00c4rzt*innen verdoppelte es die Wahrscheinlichkeit f\u00fcr Burnout [12]. Bei Erstsemestern hing anhaltendes Impostor-Erleben mit geringerem Selbstmitgef\u00fchl und mehr psychischer Belastung zusammen [3]. Wer merkt, dass die Zweifel nicht mehr nur vor Pr\u00fcfungen kommen, sondern den Alltag bestimmen, sollte das ernst nehmen und die Beratungsangebote der Universit\u00e4t nutzen. Die sind genau daf\u00fcr da.

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Was hilft

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Noch 2020 stellte das gr\u00f6\u00dfte systematische Review zum Thema fest, dass es keine einzige evaluierte Ma\u00dfnahme gegen das Impostor-Ph\u00e4nomen gab [13]. Seitdem hat sich einiges getan.

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Am besten belegt ist Gruppencoaching. In zwei randomisierten Studien mit zusammen mehr als 1.100 \u00c4rztinnen in Weiterbildung senkte ein sechsmonatiges Online-Programm Impostor-Werte und emotionale Ersch\u00f6pfung und st\u00e4rkte das Selbstmitgef\u00fchl [14, 15]. Ein Umbrella-Review von 2026, das 16 \u00dcbersichtsarbeiten zusammenfasst, sieht Potenzial in Coaching, Online-Modulen und achtsamkeitsbasierten Ans\u00e4tzen, mahnt aber, dass hochwertige Interventionsstudien noch selten sind [16].

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F\u00fcr den Studienstart ist ein anderer Befund vielleicht wichtiger. Schon ein einzelner Workshop, in dem Erstsemester das Ph\u00e4nomen kennenlernen und merken, dass es fast allen so geht, ver\u00e4ndert etwas. Nach einem solchen Workshop konnten neun von zehn Erstsemestern das Muster bei sich selbst erkennen [17], und in einer Orientierungswoche sank der Anteil mit starken Impostor-Gef\u00fchlen um zehn Prozentpunkte [18]. Der Wirkmechanismus hei\u00dft Normalisierung. Das Gef\u00fchl, allein damit zu sein, ist ein gro\u00dfer Teil des Problems, und es l\u00f6st sich in dem Moment auf, in dem die Nachbarin im H\u00f6rsaal dasselbe erz\u00e4hlt. Strukturierte Peer-Treffen f\u00fcr Studienanf\u00e4nger*innen zielen genau darauf [19].

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Was Ihr selbst tun k\u00f6nnt, l\u00e4sst sich aus dieser Evidenz ableiten. Redet dar\u00fcber, mit Kommiliton*innen und mit Lehrenden, denn die Wahrscheinlichkeit, dass Euer Gegen\u00fcber es kennt, liegt bei etwa f\u00fcnfzig Prozent. Schreibt Euch auf, was Ihr gut k\u00f6nnt, nicht nur, was Ihr noch nicht k\u00f6nnt, denn der Impostor-Kreislauf lebt davon, Erfolge zu vergessen. Und wechselt den Vergleichsma\u00dfstab. Die Frage ist nicht, ob Ihr besser seid als die Person neben Euch, sondern ob Ihr mehr k\u00f6nnt als vor vier Wochen.

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\nTippF\u00fcr Statistik-Interessierte \u2014 die Zahlen hinter dem Impostor-Ph\u00e4nomen\n
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Die meisten Studien nutzen die Clance Impostor Phenomenon Scale (CIPS, 20 Items, Wertebereich 20 bis 100). Ab 62 Punkten gelten Impostor-Gef\u00fchle als \"h\u00e4ufig\", ab 81 als \"intensiv\". Diese Grenzen sind Konvention, nicht Diagnosekriterium, und sie erkl\u00e4ren einen Teil der Streuung zwischen den Studien.

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Zwei Metaanalysen, ein Bild. Omar et al.\u00a0poolten 34 Studien mit 9.550 Medizinstudierenden und fanden eine Pr\u00e4valenz von 49 % (95 %-KI 43 bis 54 %, I\u00b2 = 95,6 %). Frauen lagen bei 51 %, M\u00e4nner bei 40 % (p = 0,021). Mit der CIPS ergaben sich 53 %, mit der Young Impostor Scale 38 % [1]. Vera-Ponce et al.\u00a0poolten 26 CIPS-Studien mit 9.110 Studierenden und kamen auf 54,2 % (95 %-KI 47,0 bis 61,3 %, I\u00b2 = 98 %), ohne Unterschied zwischen vorklinischem (48,9 %) und klinischem Abschnitt (46,8 %, !) und ohne zeitlichen Trend zwischen 2018 und 2024 [2]. Bei I\u00b2-Werten \u00fcber 95 % beschreibt der gepoolte Wert eine Gr\u00f6\u00dfenordnung, keine gemeinsame Realit\u00e4t.

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Der Studienstart in Zahlen. Rosenthal et al.\u00a0befragten 257 Erstsemester zu Beginn und am Ende des ersten Jahres. 87 % hatten anfangs hohe oder sehr hohe Werte, die bis zum Jahresende signifikant anstiegen (p < 0,001). Hohe Werte gingen mit deutlich geringerem Selbstmitgef\u00fchl einher (d = 1,62) [3]. Houseknecht et al.\u00a0beobachteten 110 Studierende \u00fcber drei Jahre und fanden steigende Impostor-Werte (p = 0,011) bei sinkender professioneller Identifikation [20]. Kim et al.\u00a0verfolgten eine Kohorte von der Orientierungswoche bis zum Ende des 16-monatigen vorklinischen Abschnitts. Der mittlere CIPS-Wert blieb praktisch unver\u00e4ndert (68,3 gegen\u00fcber 68,1), die Ausl\u00f6ser verschoben sich aber vom Zulassungsgl\u00fcck zum Vergleich mit anderen [21].

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Europ\u00e4ische Stichproben. Unter 457 schwedischen Medizinstudierenden lagen 58,4 % \u00fcber dem CIPS-Grenzwert, Frauen mit 67,4 gegen\u00fcber 59,3 Punkten (d = 0,47). Resilienz korrelierte moderat negativ mit Impostor-Werten (r = \u22120,41) [22]. In Ume\u00e5 lagen 64 % von 968 Studierenden verschiedener F\u00e4cher \u00fcber dem Grenzwert, und weder Semester noch Alter machten einen Unterschied [23]. F\u00fcr Deutschland gibt es bislang keine vergleichbare Erhebung.

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Umgebung und Ranking. Franchi und Russell-Sewell fanden bei 191 britischen Studierenden einen mittleren CIPS-Wert von 65,8, bei 65,4 % \u00fcber dem Grenzwert; pro Dezil weiter unten im Pr\u00fcfungsranking stieg der Wert um 1,12 Punkte (p < 0,05) [7]. Bei Neufeld et al.\u00a0erkl\u00e4rte die Befriedigung der psychologischen Grundbed\u00fcrfnisse 21,8 % der Varianz, das Kompetenzerleben allein hatte ein \u03b2 von \u22120,49 [8]. Rice et al.\u00a0berichten f\u00fcr Studierende aus unterrepr\u00e4sentierten Gruppen an \u00fcberwiegend wei\u00dfen Fakult\u00e4ten eine Odds Ratio von 2,75 (95 %-KI 1,65 bis 4,58) gegen\u00fcber historisch schwarzen Hochschulen [9]. In der britischen Unfallchirurgie lagen Trainees bei 70,6 Punkten, Consultants bei 59,8 [10].

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Folgen. Bei 269 \u00c4rzt*innen in Weiterbildung war das Impostor-Erleben ein unabh\u00e4ngiger Risikofaktor f\u00fcr Angst (RR = 3,64; 95 %-KI 1,96 bis 6,76) und Burnout (RR = 1,82; 95 %-KI 1,07 bis 3,08) [11]. Bei 3.116 US-\u00c4rzt*innen war intensives Impostor-Erleben mit h\u00f6heren Odds f\u00fcr Burnout (OR = 2,13; 95 %-KI 1,43 bis 3,19) und f\u00fcr Suizidgedanken (OR = 2,62; 95 %-KI 1,46 bis 4,65) verbunden [12]. Bei 226 Medizinstudierenden vermittelte das Impostor-Ph\u00e4nomen den Zusammenhang zwischen maladaptivem Perfektionismus und Suizidgedanken (indirekter Effekt B = 0,07; 95 %-KI 0,03 bis 0,13); das ist eine Mediation in Querschnittsdaten, keine Kausalkette [24].

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Interventionen. Fainstad et al.\u00a0randomisierten 101 Assistenz\u00e4rztinnen; das Impostor-Ma\u00df sank in der Coaching-Gruppe um 1,16 Punkte und stieg in der Kontrollgruppe um 0,11 (p = 0,003) [14]. Die multizentrische Replikation mit 1.017 Teilnehmerinnen fand eine Differenz von \u22121,28 Punkten (95 %-KI \u22121,63 bis \u22120,93) [15]. Nach zw\u00f6lf Monaten war der Impostor-Effekt nicht mehr signifikant (p = 0,081), das Selbstmitgef\u00fchl blieb verbessert [25]. Ein systematisches Review von sechs Online-Interventionen fand nur zwei RCTs [26]. Die Orientierungswochen-Workshops sind unkontrollierte Vorher-Nachher-Vergleiche, mit 53 % gegen\u00fcber 43 % mit h\u00e4ufigem oder intensivem Impostor-Erleben bei 222 Studierenden [18], 91,6 % Wiedererkennung bei 49 Erstsemestern [17], 96 % bei 21 Assistenz\u00e4rzt*innen [27].

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Was wir (noch) nicht wissen

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Fazit

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\nHinweisTransparenzkasten\n
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Transparenzhinweis:

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  • Interessenkonflikte: Keine angegeben.
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  • Finanzierung: Keine Angabe.
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  • KI-Nutzung: Claude (Anthropic) wurde zur strukturellen Konzeption und zur sprachlichen Bearbeitung auf Basis eines vom Autor verfassten und immer wieder \u00fcberarbeiteten Gedankengangs eingesetzt.
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  • Eigene Beteiligung: Der Autor ist in der medizinischen Ausbildungsforschung t\u00e4tig und hat auch mal Medizin studiert. Obwohl er heute Arzt und Professor ist, ist er im Studium durch Pr\u00fcfungen durchgefallen und kennt das Impostor-Gef\u00fchl sehr gut (auch wenn er das damals nicht so sch\u00f6n benennen konnte).
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Referenzen

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\n1. Omar YM, Khattab YA, Abdelmageed A, Messak M, Mandour Y, Shabeeb AE, u.\u00a0a. The impostor phenomenon construct in medical education: a meta-analysis of its prevalence and a critical appraisal of its measurement. Advances in Health Sciences Education. 2026. https://doi.org/10.1007/s10459-026-10513-3.\n
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\n2. Vera-Ponce VJ, Huaman-Vega CH, Zuzunaga-Montoya FE, Guerrero Uceda CI, Le\u00f3n-Figueroa DA, Rivera-Lozada O, u.\u00a0a. Global prevalence of impostor phenomenon in medical students: A systematic review and meta-analysis. PLOS One. 2026;21:e0351713.\n
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\n3. Rosenthal S, Schlussel Y, Yaden MB, DeSantis J, Trayes K, Pohl C, u.\u00a0a. Persistent Impostor Phenomenon Is Associated With Distress in Medical Students. Family Medicine. 2021;53:118\u201322.\n
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\n4. Clance PR, Imes SA. The imposter phenomenon in high achieving women: Dynamics and therapeutic intervention. Psychotherapy: Theory, Research &amp; Practice. 1978;15:241\u20137.\n
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\n5. Feenstra S, Begeny CT, Ryan MK, Rink FA, Stoker JI, Jordan J. Contextualizing the Impostor \"Syndrome\". Frontiers in Psychology. 2020;11.\n
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\n6. Thomas M, Bigatti S. Perfectionism, impostor phenomenon, and mental health in medicine: a literature review. International Journal of Medical Education. 2020;11:201\u201313.\n
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\n7. Franchi T, Russell-Sewell N. Medical Students and the Impostor Phenomenon: A Coexistence Precipitated and Perpetuated by the Educational Environment? Medical Science Educator. 2022;33:27\u201338.\n
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\n8. Neufeld A, Babenko O, Lai H, Svrcek C, Malin G. Why Do We Feel Like Intellectual Frauds? A Self-Determination Theory Perspective on the Impostor Phenomenon in Medical Students. Teaching and Learning in Medicine. 2022;35:180\u201392.\n
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\n9. Rice J, Rosario-Williams B, Williams F, West-Livingston L, Savage D, Wilensky JA, u.\u00a0a. Impostor syndrome among minority medical students who are underrepresented in medicine. Journal of the National Medical Association. 2023;115:191\u20138.\n
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\n10. Kamran Siddiqui Z, Tomlinson J, Scantlebury A, Jayasuriya R, Church H, Grove A. Hidden barriers to leadership: a cross-sectional survey of prevalence and predictors of Imposter Phenomenon in Trauma and Orthopaedic surgery in the UK. BMJ Open. 2025;15:e100557.\n
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\n11. Liu RQ, Davidson J, Van Hooren TA, Van Koughnett JAM, Jones S, Ott MC. Impostorism and anxiety contribute to burnout among resident physicians. Medical Teacher. 2022;44:758\u201364.\n
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\n12. Shanafelt TD, Dyrbye LN, Sinsky C, Trockel M, Makowski MS, Tutty M, u.\u00a0a. Imposter Phenomenon in US Physicians Relative to the US Working Population. Mayo Clinic Proceedings. 2022;97:1981\u201393.\n
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\n13. Bravata DM, Watts SA, Keefer AL, Madhusudhan DK, Taylor KT, Clark DM, u.\u00a0a. Prevalence, Predictors, and Treatment of Impostor Syndrome: a Systematic Review. Journal of General Internal Medicine. 2019;35:1252\u201375.\n
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\n14. Fainstad T, Mann A, Suresh K, Shah P, Dieujuste N, Thurmon K, u.\u00a0a. Effect of a Novel Online Group-Coaching Program to Reduce Burnout in Female Resident Physicians: A Randomized Clinical Trial. JAMA Network Open. 2022;5:e2210752.\n
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\n15. Mann A, Shah AN, Thibodeau PS, Dyrbye L, Syed A, Woodward MA, u.\u00a0a. Online Well-Being Group Coaching Program for Women Physician Trainees: A Randomized Clinical Trial. JAMA Network Open. 2023;6:e2335541.\n
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\n16. Gisselbaek M, Seyour M, Saxena S, Berger\u2010Estilita J, LaDonna KA, Elia N, u.\u00a0a. Rethinking the impostor phenomenon: An umbrella review of concept, context and interventions. Medical Education. 2025;60:607\u201324.\n
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\n17. Wrench A, Padilla M, O'Malley C, Levy A. Impostor phenomenon: Prevalence among 1st year medical students and strategies for mitigation. Heliyon. 2024;10:e29478.\n
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\n18. Kim E, Dupont J, Durning SJ, Landoll R, Soh M. Mitigating Impostor Phenomenon of Onboarding Military Medical Students: A Workshop Utilizing Situated Learning Theory. Military Medicine. 2025;190:e2153\u20139.\n
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\n20. Houseknecht VE, Roman B, Stolfi A, Borges NJ. A Longitudinal Assessment of Professional Identity, Wellness, Imposter Phenomenon, and Calling to Medicine Among Medical Students. Medical Science Educator. 2019;29:493\u20137.\n
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\n21. Kim E, Dupont J, Durning SJ, Bulaklak J, Crosier A, Soh M. Exploring Impostor Phenomenon During Pre-Clerkship Period in Military Medical School. Military Medicine. 2025;191:e413\u201320.\n
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\n23. Jansson A, Boman J, Sch\u00e9le I, Holmstr\u00f6m S, Rozental A, Semb O, u.\u00a0a. Impostor phenomenon and its association with perceived stress and anxiety among students in medical and social sciences at a Swedish university. Frontiers in Medicine. 2025;12.\n
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\n24. Brennan-Wydra E, Chung HW, Angoff N, ChenFeng J, Phillips A, Schreiber J, u.\u00a0a. Maladaptive Perfectionism, Impostor Phenomenon, and Suicidal Ideation Among Medical Students. Academic Psychiatry. 2021;45:708\u201315.\n
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\n25. Fainstad T, Syed A, Thibodeau PS, Vinaithirthan V, Jones CD, Mann A. Long-Term Impact of an Online Physician Group-Coaching Program to Improve Burnout and Self-Compassion in Trainees. Journal of Healthcare Management. 2024;69:414\u201323.\n
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\n26. Hsu C-L, Liu C-H, Huang C-C, Chen H-L, Chiu Y-L, Yang C-W. The effectiveness of online educational interventions on impostor syndrome and burnout among medical trainees: a systematic review. BMC Medical Education. 2024;24.\n
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\n27. Baumann N, Faulk C, Vanderlan J, Chen J, Bhayani RK. Small-Group Discussion Sessions on Imposter Syndrome. MedEdPORTAL. 2020. https://doi.org/10.15766/mep_2374-8265.11004.\n
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\n28. Mak KKL, Kleitman S, Abbott MJ. Impostor Phenomenon Measurement Scales: A Systematic Review. Frontiers in Psychology. 2019;10.\n
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Wiederverwendung

CC BY 4.0

Zitat

Mit BibTeX zitieren:
@misc{friederichs2026,\n  author = {Friederichs, Hendrik},\n  title = {Das Impostor-Ph\u00e4nomen \u2013 was mache ich hier?},\n  date = {2026-09-10},\n  url = {https://medical-education.pages.ub.uni-bielefeld.de/research/mes-blog/posts/2026-09-10-impostor/},\n  doi = { 10.59350/0vw9m-k3092},\n  langid = {de}\n}\n
Bitte zitieren Sie diese Arbeit als:
\n1. Friederichs H. Das\nImpostor-Ph\u00e4nomen \u2013 was mache ich hier? 2026.\n
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JAMA Network Open, 5(5), e2210752."},{"id":"https://doi.org/10.1001/jamanetworkopen.2023.35541","unstructured":"Mann, A., Shah, A. N., Thibodeau, P. S., Dyrbye, L., Syed, A., Woodward, M. A., Thurmon, K., Jones, C. D., Dunbar, K. S., & Fainstad, T. (2023). Online Well-Being Group Coaching Program for Women Physician Trainees. JAMA Network Open, 6(10), e2335541."},{"id":"https://doi.org/10.1111/medu.70076","unstructured":"Gisselbaek, M., Seyour, M., Saxena, S., Berger\u2010Estilita, J., LaDonna, K. A., Elia, N., & Savoldelli, G. L. (2025). Rethinking the impostor phenomenon: An umbrella review of concept, context and interventions. Medical Education."},{"id":"https://doi.org/10.1016/j.heliyon.2024.e29478","unstructured":"Wrench, A., Padilla, M., O'Malley, C., & Levy, A. (2024). Impostor phenomenon: Prevalence among 1st year medical students and strategies for mitigation. 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BMC Medical Education, 24(1)."},{"id":"https://doi.org/10.15766/mep_2374-8265.11004","unstructured":"Baumann, N., Faulk, C., Vanderlan, J., Chen, J., & Bhayani, R. K. (2020). Small-Group Discussion Sessions on Imposter Syndrome. MedEdPORTAL."},{"id":"https://doi.org/10.3389/fpsyg.2019.00671","unstructured":"Mak, K. K. L., Kleitman, S., & Abbott, M. J. (2019). Impostor Phenomenon Measurement Scales: A Systematic Review. Frontiers in Psychology, 10."}],"rid":"sy0q1-4yg31","summary":" Im Oktober beginnen viele junge Menschen ihr Medizinstudium. Viele von ihnen werden in den ersten Wochen denselben Gedanken haben, n\u00e4mlich dass alle anderen im H\u00f6rsaal besser vorbereitet, kl\u00fcger und sicherer wirken als sie selbst. Dieser Gedanke hat einen Namen, er ist gut untersucht, und er ist erstaunlich verbreitet. Der Gedanke in der ersten Woche Die allererste Vorlesung.","tags":["Studierende","Studienstart","Wohlbefinden","Lernen"],"title":"Das Impostor-Ph\u00e4nomen \u2013 was mache ich hier?","updated_at":1789025415,"url":"https://medical-education.pages.ub.uni-bielefeld.de/research/mes-blog/posts/2026-09-10-impostor/","version":"v1"}}],"items":[{"authors":[{"contributor_roles":[],"family":"Eden","given":"Terence","url":"https://orcid.org/0000-0002-9265-9069"}],"blog":{"authors":null,"community_id":"61ce553a-bafd-4aba-a952-d3bab5e85bcc","created":1788652800,"current_feed_url":null,"description":"Regular nonsense about tech and its effects \ud83d\ude43","doi":"https://doi.org/10.59350/shkspr","favicon":"https://rogue-scholar.org/api/communities/61ce553a-bafd-4aba-a952-d3bab5e85bcc/logo","feed_format":"application/atom+xml","feed_url":"https://shkspr.mobi/blog/feed/atom/?cat=-1982&HTTP_REFERER=DOI","filter":null,"generator":"WordPress","home_page_url":"https://shkspr.mobi/blog","issn":"2753-1570","language":"eng","license":"https://creativecommons.org/licenses/by/4.0/legalcode","prefix":"10.59350","relative_url":null,"secure":true,"slug":"shkspr","status":"active","subfield":"1712","title":"Terence Eden's Blog","updated":1789040050,"use_api":false},"blog_name":"Terence Eden's Blog","blog_slug":"shkspr","content_html":"

For years, I've had a test-card at the start of my slides. Before I start my talk, I can immediately see if the aspect ratio is wrong, colours are off, or any other visual issues with the presentation.

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A few years ago I was invited to give a talk and was assured that the venue was set up for audio as well as video. I dutifully filled my slides with with demo videos containing sound. None of them worked. Somewhere between the HDMI output of the presentation laptop and the speakers, the audio went AWOL.

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Ever since then, I've placed an audio test slide at the start of my presentations. There's a good range of videos on YouTube - pick one you like, embed it into your slides, and play it before your talk starts.

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Over the years, I've found the following \"bugs\" with event AV setups:

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Whether events are professionally run or community managed, you can never guarantee that sound will work. Add subtitles to your videos. If possible, add a sign-language interpreter. And, if all else fails, hold your microphone to your laptop's speakers.

\n\"\"","doi":"https://doi.org/10.59350/gm6k5-zfd63","guid":"https://shkspr.mobi/blog/?p=68346","image":"https://shkspr.mobi/blog/wp-content/uploads/2017/10/Test-Card-on-a-screen.jpg","language":"en","license":"https://creativecommons.org/licenses/by/4.0/legalcode","published_at":1788998400,"rid":"na75e-q2e41","summary":"For years, I've had a test-card at the start of my slides. Before I start my talk, I can immediately see if the aspect ratio is wrong, colours are off, or any other visual issues with the presentation. A few years ago I was invited to give a talk and was assured that the venue was set up for audio as well as video. I dutifully filled my slides with with demo videos containing sound.","tags":["Presentations"],"title":"Put an AV test at the start of your slides","updated_at":1789119908,"url":"https://shkspr.mobi/blog/2026/09/put-an-av-test-at-the-start-of-your-slides/","version":"v1"},{"authors":[{"contributor_roles":[],"name":"Ko-AutorInnen"}],"blog":{"authors":null,"community_id":"ad6b31bb-31f3-4277-bcf1-7bc662d83893","created":1740441600,"current_feed_url":null,"description":"Netzwerk Fluchtforschung ist ein multi-disziplin\u00e4res Netzwerk von Wissenschaftler*innen die zu jeglichen Aspekten von Flucht und Fl\u00fcchtlingsschutz forschen.","doi":"https://doi.org/10.59350/fluchtforschung","favicon":"https://rogue-scholar.org/api/communities/ad6b31bb-31f3-4277-bcf1-7bc662d83893/logo","feed_format":"application/atom+xml","feed_url":"https://fluchtforschung.net/feed/atom/","filter":null,"generator":"WordPress","home_page_url":"https://fluchtforschung.net/","issn":null,"language":"deu","license":"https://creativecommons.org/licenses/by/4.0/legalcode","prefix":"10.59350","relative_url":null,"secure":true,"slug":"fluchtforschung","status":"active","subfield":"3312","title":"Netzwerk Fluchtforschung","updated":1789113368,"use_api":true},"blog_name":"Netzwerk Fluchtforschung","blog_slug":"fluchtforschung","content_html":"

Der Ende Juli verabschiedete Regierungsentwurf des KI-Migrationsverwaltungsgesetzes (KIMVG) will eine breite Rechtsgrundlage f\u00fcr den Einsatz von K\u00fcnstlicher Intelligenz (KI) in Visa-, Aufenthalts- und Asylverfahren schaffen. Der Gesetzesentwurf sieht vor, personenbezogene Daten f\u00fcr die Entwicklung eigener KI-Systeme zu verarbeiten, Antr\u00e4ge automatisiert mit \u00f6ffentlich zug\u00e4nglichen Internetquellen abzugleichen und ein KI-gest\u00fctztes Verfahrensmonitoring einzuf\u00fchren. Die Bundesregierung begr\u00fcndet das Gesetz mit dem Verweis auf knappe Ressourcen und dem Ziel, Effizienz, Qualit\u00e4t und Sicherheit der Verfahren zu verbessern. Gleichzeitig weisen zivilgesellschaftliche Akteur*innen auf rechtliche L\u00fccken, zu weitreichende Befugnisse und eine Vielzahl offener Fragen hin. Dieser Blogpost analysiert die Grundelemente des KIMVG, gibt einen \u00dcberblick \u00fcber die Einsch\u00e4tzungen und Kritik der Zivilgesellschaft und diskutiert die Wichtigkeit einer breiten gesellschaftlichen Beteiligung bei der Diskussion \u00fcber die Regulierung von KI-Systemen in der Migrations- und Asylverwaltung.

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Am 29.07.2026 beschloss das Bundeskabinett den Regierungsentwurf des sogenannten KI-Migrationsverwaltungsgesetzes (KIMVG), der zu einer Weichenstellung f\u00fcr die Zukunft der deutschen Asyl- und Migrationsverwaltung werden k\u00f6nnte. Mit \u00c4nderungen und Erg\u00e4nzungen des Asylgesetzes und des Aufenthaltsgesetzes will der Entwurf eine breite Rechtsgrundlage f\u00fcr den Einsatz von KI in der Migrationsverwaltung schaffen, konkret bei Visa-, Aufenthalts- und Asylverfahren. Dies betrifft insbesondere drei Punkte: Erstens, ein \"automatisiertes Verfahrensmonitoring\", bei dem abgeschlossene Verfahren KI-gest\u00fctzt ausgewertet werden sollen, um Entscheidungsstrukturen zu identifizieren und Potenziale f\u00fcr Standardisierung und Beschleunigung zu erkennen. Zweitens \u2013 bei begr\u00fcndeten Zweifeln \u2013 ein automatisierter Abgleich von Angaben mit Quellen aus dem Internet, zum Beispiel aus sozialen Netzwerken. Drittens, eine Nutzung von personenbezogenen Daten, um beh\u00f6rdliche KI-Systeme zuk\u00fcnftig zu trainieren, zu validieren und zu testen. Das beim Bundesministerium des Inneren (BMI) angesiedelte Gesetzgebungsverfahren geht auf ein Eckpunktepapier des BMI und des Ausw\u00e4rtigen Amts (AA) von 2025 zur\u00fcck. Nach Ver\u00f6ffentlichung des ersten Referentenentwurfs des KIMVG am 25.06.2026 wurden eine Reihe von Verb\u00e4nden und zivilgesellschaftlicher Organisationen um Stellungnahme innerhalb einer Woche gebeten. Die Kurzfristigkeit wurde von allen stellungnehmenden Akteur*innen kritisiert. Der Deutsche Caritasverband e.V. schreibt beispielsweise, dass \"eine vertiefte fachliche und rechtliche Pr\u00fcfung des Entwurfs [angesichts der au\u00dferordentlich kurzen Frist] nicht m\u00f6glich war\". Als n\u00e4chste Schritte im Gesetzgebungsverfahren folgen Abstimmungen im Bundestag und Bundesrat \u2013 eine genaue Timeline ist jedoch zum aktuellen Zeitpunkt ungewiss.

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Was versteht die Bundesregierung als zentrales Problem?

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Bereits das Eckpunktepapier von AA und BMI von 2025 begr\u00fcndet die Notwendigkeit f\u00fcr KI und Automatisierung mit Verweis auf \"gesteigerte Effizienz\" und \"mehr Sicherheit\". Durch (Teil-)Automatisierung sollen Verfahren \"schneller und weniger ressourcenintensiv\" und Wartezeiten verk\u00fcrzt werden, wodurch insbesondere die Fachkr\u00e4fteeinwanderung profitiere. Ebenso verweist der Regierungsentwurf des KIMVG auf \"stetig steigende Antragsaufkommen\", begrenzte personelle und organisatorische Kapazit\u00e4ten, sowie eine uneinheitliche Verwaltungspraxis und Rechtsanwendung. Das Gesetz solle nun einen \"rechtssicheren und datenschutzkonformen Rahmen\" schaffen, um \"durch den Einsatz digitaler Verfahren \u2013 insbesondere K\u00fcnstlicher Intelligenz \u2013 die Effizienz, Einheitlichkeit, Qualit\u00e4t und Sicherheit\" der Verfahren zu erh\u00f6hen.

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Der Regierungsentwurf des KIMVG wird damit durchg\u00e4ngig mit einer bestimmten Problemdiagnose begr\u00fcndet: Komplexe rechtliche Vorgaben, die Vielzahl von Antragsstrecken und Antr\u00e4gen f\u00fchrten zu einer uneinheitlichen Verwaltungspraxis; ohne strukturelle Anpassungen sei angesichts begrenzter Ressourcen eine zus\u00e4tzliche Belastung der Verfahren absehbar. Diese Diagnose trifft ein reales Problem: Der \u00f6ffentliche Dienst in Deutschland und insbesondere die Ausl\u00e4nderbeh\u00f6rden leiden unter Personalmangel, und langwierige Verfahren belasten sowohl Antragsstellende als auch die zust\u00e4ndigen Beamt*innen. Was die Antragszahlen betrifft, ist die Faktenlage jedoch weniger eindeutig. Die Gesamtzahl der Asylantr\u00e4ge beispielsweise sank von 330.000 im Jahr 2023 auf rund 130.000 im Jahr 2025.

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Vor diesem Hintergrund ist es bemerkenswert, dass der Entwurf KI als einzig denkbare und kostenneutrale L\u00f6sung darstellt und dabei zus\u00e4tzliche Ressourcen f\u00fcr die Ausl\u00e4nderbeh\u00f6rden oder vereinfachte Verfahrensregeln als Alternativen ebenso ausblendet wie die Kosten, die mit der Einf\u00fchrung von KI einhergehen werden. Die Forschung warnt vor der Annahme, dass die Einf\u00fchrung von KI in der \u00f6ffentlichen Verwaltung automatisch Kosteneinsparungen und Effizienzgewinne mit sich bringt. Wie auch die Deutsche Vereinigung f\u00fcr Datenschutz (DVD) in ihrer Stellungnahme zum Regierungsentwurf anmerkt, erfordert eine weitergehende Digitalisierung und die Einf\u00fchrung von KI in der deutschen Migrationsverwaltung zun\u00e4chst zus\u00e4tzliches Personal, Schulungen und technische Infrastruktur \u2013 Kosten, die der Entwurf nicht ber\u00fccksichtigt. Die Argumentation im Entwurf steht f\u00fcr eine allgemeinere Tendenz, ein im Kern politisches Problem \u2013 Personalmangel, Ressourcenverteilung, komplexe verwaltungs- und rechtstechnische Sachverhalte \u2013 vorrangig durch neue Technologie l\u00f6sen zu wollen.

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Was kritisieren Interessengruppen und Zivilgesellschaft?

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Im Rahmen des Gesetzgebungsprozesses ver\u00f6ffentlichte das BMI sechs Stellungnahmen von Bundesvereinigungen, Verb\u00e4nden und B\u00fcrgerrechtsorganisationen: der AWO Bundesverband e.V., die Bundesvereinigung der kommunalen Spitzenverb\u00e4nde, die Deutsche Vereinigung f\u00fcr Datenschutz (DVD) e.V., der Deutsche Caritasverband e.V., Pro Asyl sowie Statefree e.V. Dar\u00fcber hinaus kommentierten weitere Akteur*innen den Gesetzesentwurf auf ihren eigenen Webseiten, wie beispielsweise netzpolitik.org, AlgorithmWatch oder auch die Gesellschaft f\u00fcr Informatik e.V.

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Mehrere Verb\u00e4nde erkennen an, dass die Digitalisierung der Migrationsverwaltung dringend n\u00f6tig ist, um Verfahren zu beschleunigen. Dennoch dominiert in den Stellungnahmen eine eher kritische Haltung, insbesondere mit Blick auf drei Punkte: (1) den fehlenden und unzureichenden Rechtsschutz; (2) Risiken von Diskriminierung und Bias; und (3) die Vagheit des Entwurfs, auch hinsichtlich der Entscheidungsmacht von KI-Systemen.

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Ein erster Kritikpunkt, der sich durch nahezu alle Stellungnahmen der Verb\u00e4nde zieht, betrifft die Vereinbarkeit mit Datenschutz, Verfassungsrecht und EU-Recht. Mehrere Verb\u00e4nde \u00e4u\u00dfern datenschutzrechtliche Bedenken, da die Nutzung personenbezogener Daten insgesamt zu umfassend sei. Der Entwurf erlaubt, unter bestimmten Umst\u00e4nden, auch die Verwendung nicht anonymisierter Daten. Hinsichtlich des Verfahrensmonitorings sollen selbst biometrische Daten weiterverarbeitet werden k\u00f6nnen, wenn ihre Aussonderung \"technisch unm\u00f6glich ist oder unverh\u00e4ltnism\u00e4\u00dfig hohen technischen Aufwand erfordert\". Auch ist fraglich, ob sensible, personenbezogene Daten wieder vollst\u00e4ndig gel\u00f6scht werden k\u00f6nnen, nachdem sie f\u00fcr die Entwicklung von KI-Systemen und insbesondere von Large Language Models (LLMs) genutzt wurden \u2013 Modelle, die basierend auf gro\u00dfen Datenmengen darauf abzielen, menschliche Sprache zu analysieren und zu generieren. Laut Pro Asyl verfehle der Entwurf au\u00dferdem die Anforderungen an gerechte und faire Verwaltungsverfahren im Sinne grundrechtskonformer Verfahrensgestaltung und effektiven Rechtsschutzes und schaffe stattdessen die Grundlage f\u00fcr \"intransparente, algorithmisch gesteuerte Entscheidungsprozesse\". Zwar postuliert der Entwurf, allgemein mit dem EU-Recht konform zu sein, doch werden mehreren Verb\u00e4nden und auch Wissenschaftler*innen zufolge Vorgaben hinsichtlich der EU Datenschutz-Grundverordnung (DSGVO) und der EU KI-Verordnung (KI-VO) missachtet. So beruft sich der Gesetzentwurf beispielsweise auf \u00a7 10 Abs. 3 der KI-VO, wonach Trainingsdaten \"relevant, hinreichend repr\u00e4sentativ, fehlerfrei und vollst\u00e4ndig\" sein m\u00fcssen. Wie die Deutsche Vereinigung f\u00fcr Datenschutz (DVD) in ihrer Stellungnahme betont, ist dies im Migrationskontext eine hohe H\u00fcrde: Das Ausl\u00e4nderzentralregister (AZR), das weitgehend auf denselben Datenquellen basiert, mit denen die KI sehr wahrscheinlich trainiert werden w\u00fcrde, weist bekannterma\u00dfen erhebliche Genauigkeitsdefizite auf, die dadurch versch\u00e4rft werden, dass sich viele der relevanten Merkmale schnell \u00e4ndern und veralten.

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Ein zweiter akteurs\u00fcbergreifender Kritikpunkt betrifft Fragen rund um Diskriminierung und Bias der geplanten KI-Systeme. Der Entwurf nimmt die Beh\u00f6rden in die Pflicht, keine diskriminierenden Algorithmen herauszubilden oder zu verwenden, ohne jedoch zu erl\u00e4utern, wie das sichergestellt werden soll. Konkret besteht hier ein zentrales technisches Problem: Gro\u00dfe Sprachmodelle generieren Outputs durch erlernte Muster und statistische Wahrscheinlichkeiten auf Grundlage von Trainingsdaten. Werden umfassende Daten aus bereits abgeschlossenen Verfahren als Grundlage f\u00fcr ein KI-Training genutzt, k\u00f6nnten bereits existierende Verzerrungen reproduziert werden. So k\u00f6nne die Datengrundlage bei der KI-Entwicklung je nach Auswahl diskriminierende Stereotype widerspiegeln oder festigen, warnt Pro Asyl. Eine wirksame Gegenma\u00dfnahme bestehe, der Deutschen Vereinigung f\u00fcr Datenschutz (DVD) zufolge, beispielsweise in verpflichtenden, externen und unabh\u00e4ngigen Kontrollverfahren.

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Ein dritter Kritikpunkt der Organisationen betrifft die Vagheit und mangelnde Bestimmtheit des Entwurfs, insbesondere mit Blick auf die Frage, wie viel Entscheidungsmacht KI-Systeme in Verfahren perspektivisch h\u00e4tten. Laut Entwurf verbleiben individuelle verfahrenstechnische Entscheidungen weiterhin in menschlicher Verantwortung und das BMI betont im Regierungsentwurf, dass \"die individuelle Pr\u00fcfung vollst\u00e4ndig in der Verantwortung der zust\u00e4ndigen Mitarbeitenden liege\". Hier kritisieren Verb\u00e4nde allerdings, dass unklar bleibt, wie dem sogenannten Automation-Bias vorgebeugt werden soll \u2013 also der Tendenz, maschinellen Entscheidungen eher zu vertrauen als dem menschlichen Urteil. Ohne flankierende Ma\u00dfnahmen k\u00f6nnten Entscheidungen so faktisch KI-basiert erfolgen. Die Stellungnahmen fordern hier mehrfach eine verbindliches Human-in-the-Loop-Prinzip und eine klarere Definition des Verh\u00e4ltnisses zwischen der KI-Nutzung f\u00fcr das allgemeine Verfahrensmonitoring und der Einzelfallentscheidung.

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Unklarheiten bestehen jedoch nicht nur hinsichtlich der Entscheidungsmacht, sondern ziehen sich durch den gesamten Regierungsentwurf. Die Verb\u00e4nde kritisieren, dass weitreichende Rechtsgrundlagen f\u00fcr den KI-Einsatz geschaffen werden, ohne hinreichend festzulegen, welche konkreten Systeme k\u00fcnftig f\u00fcr welche Zwecke eingesetzt werden d\u00fcrfen und wo ihre Grenzen liegen. Der AWO Bundesverband e.V. bem\u00e4ngelt entsprechend, dass von regelbasierter Dokumentenerkennung bis zur vollautomatisierten Risikoeinsch\u00e4tzung nahezu alle Szenarien denkbar seien.

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Angesichts dieser sich durch den Entwurf ziehenden Unklarheiten fordern Verb\u00e4nde teils eine intensive \u00dcberarbeitung, teils ein Zur\u00fcckziehen des Entwurfs.

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Was dar\u00fcber hinaus noch offen bleibt

\n

\u00dcber die drei zentralen Kritikpunkte der Zivilgesellschaft und Interessengruppen hinaus l\u00e4sst der Entwurf eine lange Liste weiterer Fragen unbeantwortet. Welche Transparenzma\u00dfnahmen w\u00fcrden f\u00fcr Migrantinnen und Asylbewerberinnen gelten, deren F\u00e4lle analysiert werden? Wie w\u00fcrden Sachbearbeiter*innen im Umgang mit diesen Systemen geschult? Wie lie\u00dfe sich verhindern, dass im Zuge einer uneinheitlich fortschreitenden Digitalisierung parallele, inkompatible Systeme zwischen den Beh\u00f6rden entstehen? Wie w\u00fcrden die Systeme der Komplexit\u00e4t unterschiedlicher Verfahrensarten und individueller Umst\u00e4nde gerecht werden?

\n

Bei vielen der Vorschl\u00e4ge des Entwurfs h\u00e4ngt es au\u00dferdem von der technischen Ausgestaltung und flankierenden Ma\u00dfnahmen, zum Beispiel Schulungen ab, wie rechtskonform und gewinnbringend sie f\u00fcr die Verwaltung aber auch Antragsstellende sein k\u00f6nnen. Das automatisierte Verfahrensmonitoring beispielsweise ist laut Entwurf auf die Gewinnung \"verallgemeinerungsf\u00e4higer Erkenntnisse\" ausgerichtet. Einerseits kann die Analyse vergangener Entscheidungen dazu beitragen, Inkonsistenzen, Diskriminierungsmuster oder strukturelle Fehlentwicklungen in der bisherigen Entscheidungspraxis sichtbar zu machen. Andererseits kann dieselbe Analyse eine normalisierende Wirkung entfalten, indem bestehende Entscheidungsmuster zum Ausgangspunkt f\u00fcr die Weiterentwicklung zuk\u00fcnftiger Verfahren werden. Insbesondere in Asylverfahren, in denen Anerkennungsquoten auch f\u00fcr Personen der gleichen Nationalit\u00e4t, mit \u00e4hnlichen Schutzgesuchen von politischen Faktoren beeinflusst werden und \u00fcber die Zeit variieren k\u00f6nnen, stellt sich die Frage, wie genau \"Muster\" erkannt und aktuelle Entscheidungspraktiken beeinflussen sollen.

\n

Nat\u00fcrlich l\u00e4sst sich nicht erwarten, dass ein Gesetzentwurf all diese Fragen bereits abschlie\u00dfend beantwortet. Bemerkenswert ist dennoch, wie unbestimmt der Entwurf an zentralen Stellen bleibt. Der Umfang dieser offenen Fragen ist selbst Teil der Kritik, wie auch zivilgesellschaftliche Organisationen und Wissenschaftler*innen anmerken: Ein Gesetz, das eine dauerhafte Rechtsgrundlage f\u00fcr den Einsatz von KI in der Migrationsverwaltung schaffen soll, \u00fcberl\u00e4sst zahlreiche operative Details \u2013 jene Details also, die dar\u00fcber entscheiden w\u00fcrden, ob die Systeme in der Praxis fair, nachvollziehbar und wirksam sind und wie stark KI die tats\u00e4chliche Entscheidungsfindung beeinflusst \u2013 einer sp\u00e4teren Kl\u00e4rung.

\n

 

\n

KI in der Migrationsverwaltung weiterdenken

\n

Neben Kritikpunkten an dem konkreten Gesetzentwurf kristallisieren sich auch einige grunds\u00e4tzliche Fragen sowohl zum Prozess der Gesetzfindung als auch allgemein zum Einsatz von KI in der Migrationsverwaltung heraus. In Zeiten, in denen Digitalisierung bereits ein nicht wegzudenkender Bestandteil in der Gesellschaft scheint, geht es dabei vor allem um die Frage wie diese neue Dimension der Digitalisierung gestaltet werden kann, wer dabei beteiligt werden sollte und was wir aus anderen Kontexten lernen k\u00f6nnen.

\n

Fragen dieser Tragweite w\u00fcrden eigentlich eine breite gesellschaftspolitische Debatte erfordern. Eine solche Debatte hat bislang jedoch kaum stattgefunden \u2013 die Bundesregierung treibt den Gesetzgebungsprozess stattdessen mit erkennbarem zeitlichem Druck voran, was sich auch in der kurzen Beteiligungsfrist der Verb\u00e4nde widerspiegelt. Der Zeitdruck auf Seiten der Regierung geht bereits aus dem Eckpunktepapier von AA und BMI von 2025 hervor, wenn beispielsweise ein \"schneller, wirksamer und sicherer Modernisierungserfolg\" als erkl\u00e4rtes Ziel formuliert wird. Auch sah das Papier f\u00fcr den Sommer dieses Jahres eigentlich bereits die Verabschiedung des Gesetzes durch den Bundestag vor.

\n

Dem entgegen steht die Position, wonach eine potenziell so grundlegende Neuausrichtung der Migrationsverwaltung und Entscheidungspraxis durch zentrale Akteur*innen des Politikfeldes vorbereitet und durch den Gesetzgebungsprozess hinweg begleitet werden muss. So fordert der AWO Bundesverband e.V. beispielsweise \"eine sorgf\u00e4ltige rechtliche, ethische und praktische Pr\u00fcfung\", die viele der grunds\u00e4tzlichen Fragen vor einer Einf\u00fchrung von KI-Systemen beleuchten m\u00fcsse. Konkret schl\u00e4gt der Verband deshalb eine unabh\u00e4ngige und interdisziplin\u00e4r besetzte Expert*innenkommission vor, um zun\u00e4chst zu pr\u00fcfen, \"ob und unter welchen Voraussetzungen der Einsatz von KI-Systemen in Verwaltungsverfahren mit den Anforderungen des Rechtsstaats sowie den Rechten der Betroffenen vereinbar ist\". Offen bleibt zudem, welche Akteur*innen die von KI-Systemen Betroffenen angemessen repr\u00e4sentieren k\u00f6nnen bzw. wie Migrant*innen selbst \u2013 beispielsweise durch Akteur*innen wie das Refugee Advisory Board (RAB) Germany oder die Vielzahl von Migrant*innenorganisationen\u2013 den Gesetzgebungsprozess beeinflussen k\u00f6nnen.

\n

Eine angemessene Beteiligung verschiedener Akteur*innen und eine gesellschaftspolitische Diskussion solch weitreichender Entscheidungen ist nicht nur demokratietheoretisch w\u00fcnschenswert, sondern letztlich auch f\u00fcr das Gelingen KI-gest\u00fctzter Verfahren entscheidend. Eine Vielzahl wissenschaftlicher Arbeiten hat bisherige \u2013 eher top-down initiierte \u2013 Bestrebungen, KI im Bereich Migration und Asyl einzusetzen, kritisch beleuchtet: etwa die Dialekterkennungssoftware des BAMF oder den Einsatz des Geomatch-Algorithmus in den Niederlanden, der mittlerweile bereits in der Pilotphase gestoppt wurde. Zuvor hatten Forschungsarbeiten auf die diskriminierenden Wirkweisen des zugrundeliegenden Algorithmus hingewiesen. Solche Systeme sind nicht nur mit Blick auf die Betroffenen h\u00f6chst problematisch und k\u00f6nnen zu Verletzungen von Grund- und Menschenrechten f\u00fchren, sondern k\u00f6nnen letztlich auch einen Reputationsschaden f\u00fcr die zust\u00e4ndigen Regierungen mit sich bringen.

\n

Dass KI und Digitalisierung globale Mobilit\u00e4t ma\u00dfgeblich ver\u00e4ndern und Chancen, Herausforderungen sowie Risiken f\u00fcr das Migrationsmanagement in der EU und Deutschland mit sich bringen, r\u00fcckt zunehmend in den Fokus wissenschaftlicher und gesellschaftspolitscher Debatten. Obwohl das KIMVG ein konkretes Beispiel daf\u00fcr ist, wie Gesetzgebung diese Chancen und Herausforderungen gestalten kann, findet die Auseinandersetzung bislang vor allem in Fachkreisen statt. In der breiteren \u00d6ffentlichkeit und den gro\u00dfen Medien wird der Entwurf bisher nur punktuell aufgegriffen. Das erschwert insbesondere Betroffenen \u2013 zus\u00e4tzlich zur juristischen Komplexit\u00e4t des Gesetzes \u2013 den Zugang zum Diskurs. Insgesamt macht der Entwurf deutlich, dass Fragen des KI-Einsatzes in der Migrations- und Asylverwaltung zweierlei ben\u00f6tigen: einen pr\u00e4zise formulierten und grundrechtskonformen rechtlichen Rahmen genauso wie eine grunds\u00e4tzliche gesellschaftliche Debatte dar\u00fcber, welchen Stellenwert KI und Automatisierungen in grundrechtssensiblen Verfahren haben sollten und ob und wie sie halten k\u00f6nnen, was sie versprechen.

\n

Eine englischsprachige, k\u00fcrzere Version dieses Posts wurde auf TechPolicy Press ver\u00f6ffentlicht.

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\n

A recently published article addresses[1] the long standing problem of why transition metals complexes such as e.g. Cp2TiCl2 in the presence of solutions of polysulfide dianions containing sulfur chains of various lengths, can react to form sulfur ring complexes of a specific size, depending on the metal. Thus when the early transition metal is Ti (Cp = cyclopentadienyl) it forms only the six membered ring shown below (X=S), with none of the five-membered/four-sulfur ring present. However, other central and later transition period metals only form four-sulfur rings.[1]
\n\"\"
\nThe effect was attributed to the degree of overlap\u00a0of a localised sulfur p-orbital with a vacant Ti d-orbital as shown below (Figure 1. click on the diagram to get a 3D model).

\n

\n

\"\"
\nFigure 1. Overlap between a sulfur p-donor and a titanium d-acceptor.

\n

One quantative estimate of the magnitude of the effect can be obtained using the NBO7 method[2], which provides a value for the perturbation interaction energy between the filled donor orbital (the S p-orbital) and the empty acceptor orbital (the Ti d-orbital) as a so-called E(2) energy. Thus in the article[1] the E(2) energy for the Ti six-membered complex shown above was reported as 21.2 kcal/mol (Table below) whereas for the analogous five-ring (for which the overlap between the two orbitals is less good) the value was 11.0 kcal/mol. This effect can be related [1] to the relative (free energy) stability of the product complex in the above reaction.

\n

The question now arises whether the effect can be “optimised” by changing some of the ring atoms from S to another. In fact eight crystal structures have been reported with such substitutions (Table) and so here the NBO7 analysis is repeated for these systems and a few other as yet unreported examples.

\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n\n
Table. NBO7 E(2) interaction energy for variants of Cp2TiS5.
CSD NameRing atomsNBO7 E(2)Ti-S length, \u00c5Ti-S dihedralLit/CSDMN15L/Def2-QZVPP NBO7
CYPTIS01S, S, S, S, S21.202.466, 2.47062.0[3][4]
KIVTOYS, S, Se, Se, Se21.702.47165.7[5][6]
NIRXERS, S, X=N-Me (ax)\u2020, S, S15.352.462, 2.47954.9[7], [8][9]
UnknownS, S, X=P-Me (ax), S, S23.592.45363.5unknown[10]
SEDRUOS, S, X=As-Me(ax), S, S23.492.45465.7[11][12]
SEDRUOS, S, X=As-Me(eq), S, S21.582.460, 2.47064.8\u2020[13]
FEHTOBS, S, X=Cp2TiS5, S, S\u20212.46368.9, 63.9[14][15]
VOSMUOS, S, Se, Se, Se21.702.47265.7[5], [16][17]
VOSNEZS, S,Se, Se, S19.932.463, 2.47565.1, 64.1[5], [18][19]
VOSNAVSe,Se,Se,Se,Se21.38–66.2[20],[21][22]
ZEMXIVS, Se, Se, Se, Se18.652.46767.0[23][24]
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Analysis

\n
    \n
  1. There appears to be a reasonable correction between the NBO E(2) energy and the Ti-S bond length. The shortest bond (X=PMe) corresponds to the highest E(2) value of 23.59 kcal/mol. SEDRUO is a known example (X=AsMe, Figure 2) and X=PMe is worthy of synthesis to reinforce this conclusion.
    2. \n
  2. The donation from the sulfur\u00a0p-orbital to the Ti d-orbital appears to reach a maximum at\u00a0~65\u00b0, not far off the value for Cp2TiS5 itself (Figure 1).
    3. \n
  3. The series\u00a0X=NMe, PMe, AsMe is interesting because the Me group has a favoured axial position (Figure 2), by an estimated 10.6 kcal/mol for\u00a0X=NMe. This remarkable preference is probably caused by the bond angle subtended at X, since no strong stereoelectronic effect could be found\u00a0(such as donation from the lone pair on the N/P/As).
    \n\"\"
    \nFigure 2.Structure of SEDRUO, showing the strong axial preference.
    4. \n
  4. X = Cp2TiS5 is interesting because it should exhibit the effect twice, at each Ti. Unfortunately the wavefunction for this species appears to have a pathological problem with converging to an NBO localised solution – we hope to find a solution to this at some stage. The Ti-S bond lengths however do not suggest the effect noted above will be especially high for this species.
    5. \n
  5. PUJFUV[25] replaces one six-electron Cp ligand metal donor with an apparent two-electron contribution from an 2,6-di-isopropylphenoxy ligand. This has a measured Ti-O bond length of 1.795\u00c5, which is towards the shorter end of the spectrum of Ti-O lengths (which range from ~1.7 to ~2.2\u00c5). This intriguing example will be analysed in a separate post.
    6. \n
\n

Conclusions

\n

The effect identified previously[1] which is responsible for the preference of early transition metals such as Ti to form polysulfide rings with five sulfurs rather than four appears to reach a maximum for the known species X=AsMe (Figure 2) or the as yet unmade molecule with X=PMe.

\n
\n

\u2020The equatorial isomer for X=NMe is a remarkable ~10.6 kcal/mol higher in free energy.[26] whereas for X=AsMe it is reduced to 4.59 kcal/mol. This is probably due to the angle subtended at N/As, which is 117.7\u00b0 for N and 103.6\u00b0 for As, which may also propagate to the values of the dihedral angle. \u2021The NBO7 localisation search terminated unsuccessfully after considering 100000 bonding patterns.

\n

References

\n
  1. H.S. Rzepa, and J.D. Woollins, \"Identifying the origins of the ring-size specificity of transition metals for polysulfide anions\", Dalton Transactions, 2026. https://doi.org/10.1039/d6dt01849a\n\n
    2. \n
  2. E.D. Glendening, C.R. Landis, and F. Weinhold, \"6 Natural bond orbital theory: Discovering chemistry with NBO7\", Complementary Bonding Analysis, pp. 129-156, 2021. https://doi.org/10.1515/9783110660074-006\n\n
    3. \n
  3. E. Muller, J.L. Petersen, and L.F. Dahl, \"Synthesis and characterization of Di-\u03c0-cyclopentadienyl- metal pentasulfides of titanium(IV) and vanadium (IV):an operational test of the influence of an unpaired electron on the molecular geometry\", Journal of Organometallic Chemistry, vol. 111, pp. 91-112, 1976. https://doi.org/10.1016/s0022-328x(00)87061-8\n\n
    4. \n
  4. H. Rzepa, \"CYPTIS5 MN15L/Def2-TZVPP, G = -3227.141839 Def2-QZVPP NBO\", 2026. https://doi.org/10.14469/hpc/15689\n\n
    5. \n
  5. P. Pekonen, Y. Hiltunen, R.S. Laitinen, and J. Valkonen, \"Selenium-77 NMR spectroscopic and x-ray crystallographic characterization of bis(cyclopentadienyl)titanium selenide sulfide mixtures [Ti(C5H5)2SexS5x]\", Inorganic Chemistry, vol. 30, pp. 1874-1878, 1991. https://doi.org/10.1021/ic00008a036\n\n
    6. \n
  6. H. Rzepa, \"KIVTOY MN15L/Def2-TZVPP DCM => NBO7 Def2-QZVPP\", 2026. https://doi.org/10.5281/zenodo.22270368\n\n
    7. \n
  7. R. Steudel, O. Schumann, J. Buschmann, and P. Luger, \"S4NR (R=Methyl,n-Octyl) as Novel Chelating Ligands in Titanocene Complexes and First Synthesis of Small Sulfurimide Heterocycles SnNR (n=5, 6)\", Angewandte Chemie International Edition, vol. 37, pp. 492-494, 1998. https://doi.org/10.1002/(sici)1521-3773(19980302)37:4<492::aid-anie492>3.0.co;2-a\n\n
    8. \n
  8. Steudel, R.., Schumann, O.., Buschmann, J.., and Luger, P.., \"CCDC 103650: Experimental Crystal Structure Determination\", 1998. https://doi.org/10.5517/cc3gvky\n\n
    9. \n
  9. H. Rzepa, \"NIRXER NBO7 Def2-QZVPP No solvent LP ( 2) S 4 88. BD*( 2)Ti 1- S 2 15.35\", 2026. https://doi.org/10.5281/zenodo.22141983\n\n
    10. \n
  10. H. Rzepa, \"SEDRUO (As-Me) => P-Me ax G = -3210.173356 Def2-QZVPP NBO7 LP ( 2) S 5 . BD*( 2)Ti 1- S 6 23.59\", 2026. https://doi.org/10.5281/zenodo.22664179\n\n
    11. \n
  11. R. Steudel, B. Holz, and J. Pickardt, \"Synthesis and Structure of [(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>TiS<sub>4</sub>AsCH<sub>3</sub>]\u2014a New Reagent for the Synthesis of Sulfur\u2010Rich Heterocycles\", Angewandte Chemie International Edition in English, vol. 28, pp. 1269-1271, 1989. https://doi.org/10.1002/anie.198912691\n\n
    12. \n
  12. H. Rzepa, \"SEDRUO (As-Me) NBO7 LP ( 2) S 5 BD*( 2)Ti 1- S 6 23.49\", 2026. https://doi.org/10.5281/zenodo.22286648\n\n
    13. \n
  13. H. Rzepa, \"SEDRUO (As-Me) eq NBO7 => Def2-QZVPP LP ( 2) S 4 101. BD*( 2)Ti 1- S 2 21.58\", 2026. https://doi.org/10.5281/zenodo.22669613\n\n
    14. \n
  14. D.M. Giolando, T.B. Rauchfuss, A.L. Rheingold, and S.R. Wilson, \"Chemistry of (RC5H4)2TiE5 (E = S, Se). New information on its reactions with nucleophiles, syntheses and reactions of 1,4-[(RC5H4)2Ti]2E4, and a second isomer of (RC5H4)2TiS2C2(CO2Me)2\", Organometallics, vol. 6, pp. 667-675, 1987. https://doi.org/10.1021/om00146a040\n\n
    15. \n
  15. H. Rzepa, \"FEHTOB Cp2Ti(SS)2TiCp2 NBO7 TZVPP\", 2026. https://doi.org/10.5281/zenodo.22655433\n\n
    16. \n
  16. Laasonen, Heli., Ik\u00e4heimonen, Johanna., Suomela, Mikko., Rautiainen, J. Mikko., and Laitinen, Risto S.., \"CCDC 1887988: Experimental Crystal Structure Determination\", 2019. https://doi.org/10.5517/ccdc.csd.cc21clvw\n\n
    17. \n
  17. H. Rzepa, \"VOSMUO NBO7 Def2-QZVPP no solvent LP ( 2) S 2 116. BD*( 2)Ti 1- S 6 21.70\", 2026. https://doi.org/10.5281/zenodo.22141977\n\n
    18. \n
  18. Laasonen, Heli., Ik\u00e4heimonen, Johanna., Suomela, Mikko., Rautiainen, J. Mikko., and Laitinen, Risto S.., \"CCDC 1887990: Experimental Crystal Structure Determination\", 2019. https://doi.org/10.5517/ccdc.csd.cc21clxy\n\n
    19. \n
  19. H. Rzepa, \"VOSNEZ MN15L/Def2-TZVPP DCM\", 2026. https://doi.org/10.5281/zenodo.22270375\n\n
    20. \n
  20. H. Laasonen, J. Ik\u00e4heimonen, M. Suomela, J.M. Rautiainen, and R.S. Laitinen, \"Titanocene Selenide Sulfides Revisited: Formation, Stabilities, and NMR Spectroscopic Properties\", Molecules, vol. 24, pp. 319, 2019. https://doi.org/10.3390/molecules24020319\n\n
    21. \n
  21. Laasonen, Heli., Ik\u00e4heimonen, Johanna., Suomela, Mikko., Rautiainen, J. Mikko., and Laitinen, Risto S.., \"CCDC 1887989: Experimental Crystal Structure Determination\", 2019. https://doi.org/10.5517/ccdc.csd.cc21clwx\n\n
    22. \n
  22. H. Rzepa, \"VOZNAV MN15L/Def2-QZVPP (Se only) NBO7 LP ( 2)Se 2 BD*( 2)Ti 1-Se 6 21.38\", 2026. https://doi.org/10.5281/zenodo.22286621\n\n
    23. \n
  23. C.P. Raptopoulou, A. Terzis, N. Tzavellas, and N. Klouras, \"Sulfur\u2010Selenium Chelates: Crystal structure of the first titanocene derivative Ti(\u03b7<sup>5</sup>\u2010C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>SSe<sub>4</sub>\", Zeitschrift f\u00fcr anorganische und allgemeine Chemie, vol. 621, pp. 1800-1802, 1995. https://doi.org/10.1002/zaac.19956211032\n\n
    24. \n
  24. H. Rzepa, \"ZEMXIY NBO7 Def2-QZVPP No solvent LP ( 2)Se 3 124. BD*( 2)Ti 1- S 2 18.65\", 2026. https://doi.org/10.5281/zenodo.22141970\n\n
    25. \n
  25. A.V. Firth, and D.W. Stephan, \"Monocyclopentadienyl\u2212Titanium Aryloxide Sulfide Complexes\", Inorganic Chemistry, vol. 37, pp. 4726-4731, 1998. https://doi.org/10.1021/ic9800839\n\n
    26. \n
  26. H. Rzepa, \"NIRXER Def2-TZVPP, DCM equatorial N-Me G = -2923.496304 (G = -2923.513188) DG = 10.6\", 2026. https://doi.org/10.5281/zenodo.22669635\n\n
    27. \n
\n\n
","doi":"https://doi.org/10.59350/p8zwp-39q65","guid":"https://www.ch.ic.ac.uk/rzepa/blog/?p=31892","language":"en","license":"https://creativecommons.org/licenses/by/4.0/legalcode","published_at":1788998400,"reference":[{"id":"https://doi.org/10.1039/d6dt01849a","unstructured":"Rzepa, H. S., & Woollins, J. D. (2026). Identifying the origins of the ring-size specificity of transition metals for polysulfide anions. Dalton Transactions."},{"id":"https://doi.org/10.1515/9783110660074-006","unstructured":"Glendening, E. D., Landis, C. R., & Weinhold, F. (2021). 6 Natural bond orbital theory: Discovering chemistry with NBO7. In Complementary Bonding Analysis (pp. 129\u2013156). De Gruyter."},{"id":"https://doi.org/10.1016/s0022-328x(00)87061-8","unstructured":"Muller, E. G., Petersen, J. L., & Dahl, L. F. (1976). Synthesis and characterization of Di-\u03c0-cyclopentadienyl- metal pentasulfides of titanium(IV) and vanadium (IV):an operational test of the influence of an unpaired electron on the molecular geometry. Journal of Organometallic Chemistry, 111(1), 91\u2013112."},{"id":"https://doi.org/10.14469/hpc/15689","unstructured":"Rzepa, H., Imperial College London, Imperial College Research Computing Service, & Rzepa, H. (2026). CYPTIS5 MN15L/Def2-TZVPP, G = -3227.141839 Def2-QZVPP NBO [Dataset]. Imperial College London."},{"id":"https://doi.org/10.1021/ic00008a036","unstructured":"Pekonen, P., Hiltunen, Y., Laitinen, R. S., & Valkonen, J. (1991). Selenium-77 NMR spectroscopic and x-ray crystallographic characterization of bis(cyclopentadienyl)titanium selenide sulfide mixtures [Ti(C5H5)2SexS5x]. Inorganic Chemistry, 30(8), 1874\u20131878."},{"id":"https://doi.org/10.5281/zenodo.22270368","unstructured":"Rzepa, H. (2026). KIVTOY MN15L/Def2-TZVPP DCM => NBO7 Def2-QZVPP [Dataset]. Zenodo."},{"id":"https://doi.org/10.1002/(sici)1521-3773(19980302)37:4492::aid-anie4923.0.co;2-a","unstructured":"R. Steudel, O. Schumann, J. Buschmann, and P. Luger, \"S4NR (R=Methyl,n-Octyl) as Novel Chelating Ligands in Titanocene Complexes and First Synthesis of Small Sulfurimide Heterocycles SnNR (n=5, 6)\", Angewandte Chemie International Edition, vol. 37, pp. 492-494, 1998. https://doi.org/10.1002/(sici)1521-3773(19980302)37:4<492::aid-anie492>3.0.co;2-a"},{"id":"https://doi.org/10.5517/cc3gvky","unstructured":"Steudel, R., Schumann, O., Buschmann, J., & Luger, P. (1998). CCDC 103650: Experimental Crystal Structure Determination [Dataset]. Cambridge Crystallographic Data Centre."},{"id":"https://doi.org/10.5281/zenodo.22141983","unstructured":"Rzepa, H. (2026). NIRXER NBO7 Def2-QZVPP No solvent LP ( 2) S 4 88. BD*( 2)Ti 1- S 2 15.35 [Dataset]. Zenodo."},{"id":"https://doi.org/10.5281/zenodo.22664179","unstructured":"Rzepa, H. (2026). SEDRUO (As-Me) => P-Me ax G = -3210.173356 Def2-QZVPP NBO7 LP ( 2) S 5 . BD*( 2)Ti 1- S 6 23.59 [Dataset]. Zenodo."},{"id":"https://doi.org/10.1002/anie.198912691","unstructured":"Steudel, R., Holz, B., & Pickardt, J. (1989). Synthesis and Structure of [(C5H5)2TiS4AsCH3]\u2014a New Reagent for the Synthesis of Sulfur\u2010Rich Heterocycles. Angewandte Chemie International Edition in English, 28(9), 1269\u20131271."},{"id":"https://doi.org/10.5281/zenodo.22286648","unstructured":"Rzepa, H. (2026). SEDRUO (As-Me) NBO7 LP ( 2) S 5 BD*( 2)Ti 1- S 6 23.49 [Dataset]. Zenodo."},{"id":"https://doi.org/10.5281/zenodo.22669613","unstructured":"Rzepa, H. (2026). SEDRUO (As-Me) eq NBO7 => Def2-QZVPP LP ( 2) S 4 101. BD*( 2)Ti 1- S 2 21.58 [Dataset]. Zenodo."},{"id":"https://doi.org/10.1021/om00146a040","unstructured":"Giolando, D. M., Rauchfuss, T. B., Rheingold, A. L., & Wilson, S. R. (1987). Chemistry of (RC5H4)2TiE5 (E = S, Se). New information on its reactions with nucleophiles, syntheses and reactions of 1,4-[(RC5H4)2Ti]2E4, and a second isomer of (RC5H4)2TiS2C2(CO2Me)2. Organometallics, 6(3), 667\u2013675."},{"id":"https://doi.org/10.5281/zenodo.22655433","unstructured":"Rzepa, H. (2026). FEHTOB Cp2Ti(SS)2TiCp2 NBO7 TZVPP [Dataset]. Zenodo."},{"id":"https://doi.org/10.5517/ccdc.csd.cc21clvw","unstructured":"Laasonen, H., Ik\u00e4heimonen, J., Suomela, M., Rautiainen, J. M., & Laitinen, R. S. (2019). CCDC 1887988: Experimental Crystal Structure Determination [Dataset]. Cambridge Crystallographic Data Centre."},{"id":"https://doi.org/10.5281/zenodo.22141977","unstructured":"Rzepa, H. (2026). VOSMUO NBO7 Def2-QZVPP no solvent LP ( 2) S 2 116. BD*( 2)Ti 1- S 6 21.70 [Dataset]. Zenodo."},{"id":"https://doi.org/10.5517/ccdc.csd.cc21clxy","unstructured":"Laasonen, H., Ik\u00e4heimonen, J., Suomela, M., Rautiainen, J. M., & Laitinen, R. S. (2019). CCDC 1887990: Experimental Crystal Structure Determination [Dataset]. Cambridge Crystallographic Data Centre."},{"id":"https://doi.org/10.5281/zenodo.22270375","unstructured":"Rzepa, H. (2026). VOSNEZ MN15L/Def2-TZVPP DCM [Dataset]. Zenodo."},{"id":"https://doi.org/10.3390/molecules24020319","unstructured":"Laasonen, H., Ik\u00e4heimonen, J., Suomela, M., Rautiainen, J. M., & Laitinen, R. S. (2019). Titanocene Selenide Sulfides Revisited: Formation, Stabilities, and NMR Spectroscopic Properties. Molecules, 24(2), 319."},{"id":"https://doi.org/10.5517/ccdc.csd.cc21clwx","unstructured":"Laasonen, H., Ik\u00e4heimonen, J., Suomela, M., Rautiainen, J. M., & Laitinen, R. S. (2019). CCDC 1887989: Experimental Crystal Structure Determination [Dataset]. Cambridge Crystallographic Data Centre."},{"id":"https://doi.org/10.5281/zenodo.22286621","unstructured":"Rzepa, H. (2026). VOZNAV MN15L/Def2-QZVPP (Se only) NBO7 LP ( 2)Se 2 BD*( 2)Ti 1-Se 6 21.38 [Dataset]. Zenodo."},{"id":"https://doi.org/10.1002/zaac.19956211032","unstructured":"Raptopoulou, C. P., Terzis, A., Tzavellas, N., & Klouras, N. (1995). Sulfur\u2010Selenium Chelates: Crystal structure of the first titanocene derivative Ti(\u03b75\u2010C5H5)2SSe4. Zeitschrift F\u00fcr Anorganische Und Allgemeine Chemie, 621(10), 1800\u20131802."},{"id":"https://doi.org/10.5281/zenodo.22141970","unstructured":"Rzepa, H. (2026). ZEMXIY NBO7 Def2-QZVPP No solvent LP ( 2)Se 3 124. BD*( 2)Ti 1- S 2 18.65 [Dataset]. Zenodo."},{"id":"https://doi.org/10.1021/ic9800839","unstructured":"Firth, A. V., & Stephan, D. W. (1998). Monocyclopentadienyl\u2212Titanium Aryloxide Sulfide Complexes. Inorganic Chemistry, 37(18), 4726\u20134731."},{"id":"https://doi.org/10.5281/zenodo.22669635","unstructured":"Rzepa, H. (2026). NIRXER Def2-TZVPP, DCM equatorial N-Me G = -2923.496304 (G = -2923.513188) DG = 10.6 [Dataset]. Zenodo."}],"rid":"qpjc6-7hm46","summary":"A recently published article addresses the long standing problem of why transition metals complexes such as e.g. Cp2TiCl2 in the presence of solutions of polysulfide dianions containing sulfur chains of various lengths, can react to form sulfur ring complexes of a specific size, depending on the metal.","tags":["Interesting Chemistry","Reaction Mechanism"],"title":"Identifying the origins of the ring-size specificity of transition metals for polysulfide anions: \"tuning\" the effect.","updated_at":1789111825,"url":"https://www.ch.ic.ac.uk/rzepa/blog/?p=31892","version":"v1"},{"authors":[{"affiliation":[{"name":"University of Wroc\u0142aw, Chemistry"}],"contributor_roles":[],"family":"Janeta","given":"Mateusz","url":"https://orcid.org/0000-0003-2197-7913"}],"blog":{"authors":null,"community_id":"c21eed24-c860-43d0-997c-0bc782922544","created":1788652800,"current_feed_url":null,"description":null,"doi":"https://doi.org/10.59350/silsesquioxane","favicon":"https://rogue-scholar.org/api/communities/c21eed24-c860-43d0-997c-0bc782922544/logo","feed_format":"application/atom+xml","feed_url":"https://silsesquioxane.blogspot.com/feeds/posts/default","filter":null,"generator":"Blogger","home_page_url":"https://silsesquioxane.blogspot.com/","issn":null,"language":"eng","license":"https://creativecommons.org/licenses/by/4.0/legalcode","prefix":"10.59350","relative_url":null,"secure":true,"slug":"silsesquioxane","status":"active","subfield":"1604","title":"Polyhedral Oligomeric Silsesquioxane (POSS) Chemistry","updated":1789050682,"use_api":true},"blog_name":"Polyhedral Oligomeric Silsesquioxane (POSS) Chemistry","blog_slug":"silsesquioxane","content_html":"
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Polyhedral oligomeric silsesquioxanes (POSS) have long served as more than a hybrid organic-inorganic filler for polymers. Their partially condensed silanol forms present a rigid, oxygen-rich pocket that closely resembles a fragment of amorphous silica, and this pocket is an excellent ligand for metal ions of nearly every part of the periodic table. Single-crystal X-ray diffraction has been the decisive tool for confirming what these metal-POSS assemblies actually look like, since spectroscopic and computational evidence alone can rarely distinguish between competing cage topologies. This review surveys recent crystallographically confirmed metal-POSS complexes, organized by the metal center, and closes with a synthesis of the structural trends that emerge once the diffraction data are compared side by side.

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POSS as a Ligand Platform for Metal Ions

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The starting point for nearly every metal-POSS complex discussed below is an incompletely condensed silsesquioxane, most often a trisilanol of general formula R7Si7O9(OH)3, in which R is a bulky organic substituent such as cyclohexyl, isobutyl, or phenyl.1 Deprotonation of the three remaining hydroxyl groups generates a trianionic, oxygen-donor pocket that reacts with a metal-organic precursor MR'n to cap the open corner of the cage, expelling the R' groups as volatile byproducts and leaving the metal bound in a fashion reminiscent of a tripodal ligand (Figure 1). Depending on the metal and its coordination requirements, this corner-capped unit can be a stable end point in its own right, as is typical for many main-group and alkaline-earth derivatives, or it can undergo further self-assembly into larger cage structures through bridging oxo, hydroxo, or alkoxo groups, as is the case for most of the transition metal and lanthanide complexes discussed below. Because these frameworks so closely mimic isolated surface sites on silica, they have functioned for decades as molecular models for silica-supported catalysts, and single-crystal X-ray diffraction has been essential for relating a given coordination geometry to catalytic behavior observed in solution or in the heterogeneous phase.

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\n\"Scheme\n

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Figure 1. General corner-capping strategy for forming a closed-cage metallasilsesquioxane from an open-cage trisilanol and a metal-organic precursor MR'n, where M is a metal from group 1, 2, or 13 of the periodic table, R is an unreactive alkyl or aryl substituent, and R' is an alkyl group or hydrogen.

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Nickel, Manganese, Iron, and Vanadium Cages

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Beyond copper, the same cage-forming chemistry has been extended to several other transition metals, each contributing distinctive structural motifs. A hexanuclear nickel(II) phenylsilsesquioxane, isolated as a dioxane-benzonitrile-water solvate and studied by X-ray and topological analysis, adopts an unusual cylinder-like architecture in which benzonitrile coordinates directly to the metallasilsesquioxane core, a rare mode of complexation for this ligand class.14 This complex was also tested as a catalyst for oxidations with peroxides: tert-butyl hydroperoxide converted 1-phenylethanol to acetophenone in 90 percent yield after 24 hours, whereas meta-chloroperoxybenzoic acid oxidized cyclohexane to a cyclohexanone/cyclohexanol mixture in a more modest 24 percent yield, with methylcyclohexane giving a broader spread of isomeric ketones and alcohols in comparable overall yield.14

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Figure 2. X-ray crystal structure of the cylinder-like Ni6 architecture of Bilyachenko et al., Molecules 2016, 21, 665 (ref. 14), rendered directly from the deposited crystal structure. Top view (left) shows the Ni1, Ni2, and Ni3 pairs forming the Ni6O6 ring sandwiched between the two 12-membered siloxane cycles, with the encapsulated chloride anion at the crystallographic center of inversion. Side view (right) shows the resulting cylinder shape, alongside a detail of the distorted octahedral coordination environment at one nickel center.

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Manganese chemistry has produced an especially structurally diverse series, beginning with the first heterobimetallic Mn/Na and Mn/Li derivatives reported by Lorenz, Blaurock, and Edelmann in 2008, both confirmed by single-crystal X-ray diffraction with manganese-oxygen bond lengths of 1.985(2) to 2.146(2) angstroms in the Mn/Na cage and a narrower 2.046(3) to 2.048(3) angstrom range in the Mn/Li cage. This early series was purely structural in purpose and was reported without any catalytic testing.15 More recent manganese cages incorporating 1,10-phenanthroline or bathophenanthroline ligands have revealed a still more unusual feature, the coexistence of sodium, manganese(II), and manganese(III) within a single cage, a consequence of spontaneous oxidation during self-assembly that only diffraction analysis could unambiguously confirm, with the manganese(III)-oxygen bonds consistently 0.2 to 0.3 angstroms shorter than the corresponding manganese(II)-oxygen bonds in the same cage.16,17 The phenanthroline series was synthesized specifically to evaluate manganese silsesquioxanes as precatalysts for the oxidative amidation of alcohols and aldehydes with tert-butyl hydroperoxide, and at 5 mol percent manganese loading the two simplest cages in the series gave the benzamide product in 84 and 79 percent yield, outperforming a range of simple manganese salts and oxides tested for comparison.16 The bathophenanthroline series was instead developed as a catalyst for the solvent-free cycloaddition of CO2 to epoxides, reaching a 90 percent yield of cyclic carbonate under standard conditions and up to 99 percent yield after optimizing the reaction temperature and pressure, roughly double the yield obtained with simple manganese chloride under the same conditions, and the same complexes additionally showed antifungal activity against several phytopathogenic Fusarium and related fungal species that exceeded that of the commercial fungicide triadimefon at equal concentration.17 Iron(III)-based phenylsilsesquioxane/acetylacetonate complexes reported in 2024 show a comparable sensitivity to the identity of the alkali metal template, with lithium, sodium, and potassium each directing the assembly toward a distinct cage size and silsesquioxane ring size, including the first observation of a trimeric silsesquioxane ligand within a metallasilsesquioxane cage.18 Catalytically, the Fe4Na4 congener stood out among the three, reaching a record 55 percent yield of oxygenates in the peroxidative oxidation of cyclohexane, and the series as a whole also promoted the cycloaddition of CO2 to epoxides, giving cyclic carbonates in 58 to 96 percent yield depending on the substrate.18

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Figure 3 (Fe4Na4 and Fe3K3 renders pending). X-ray crystal structure of the Fe2Li2 cage from the alkali-metal-dependent series of Bilyachenko et al., Inorg. Chem. 2024, 63, 1909-1918 (ref. 18), rendered directly from the deposited crystallographic coordinates (CCDC 2263801). The Fe4Na4 (CCDC 2267402) and Fe3K3 (CCDC 2280386) congeners from the same series will be added as companion panels once rendered.

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Vanadium chemistry has taken a different direction altogether, yielding polyoxovanadate clusters protected by silsesquioxane ligands rather than classical cage metallasilsesquioxanes. A fourteen-vanadium cluster represents the highest nuclearity yet reported for this combination, displaying vanadium-oxygen distances of 1.933 to 2.071 angstroms to the silsesquioxane ligands and considerably shorter terminal vanadium-oxo bonds of 1.519 to 1.695 angstroms, while a six-vanadium congener adopts a more regular planar hexagonal arrangement with vanadium-oxygen bonds of 1.987 to 2.006 angstroms and terminal vanadium-oxo bonds of 1.562 to 1.601 angstroms.19 The hexavanadium cluster was developed specifically as a heterogeneous catalyst for the synthesis of quinazolinones from 2-aminobenzamide and aldehydes, reaching essentially complete conversion with selectivity typically between 90 and 99 percent across a broad substrate scope of electron-rich, electron-poor, heterocyclic, and aliphatic aldehydes, and it clearly outperformed the higher-nuclearity fourteen-vanadium cluster under comparable conditions. The catalyst could be recycled for at least six successive runs with only a negligible loss of conversion and a slight decrease in selectivity, and inductively coupled plasma mass spectrometry confirmed that no more than 0.015 percent of the vanadium content leached into solution during the reaction, supporting its heterogeneous mode of action.

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Zinc-POSS Complexes: Structure and Applications in Catalysis

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Zinc occupies a smaller but catalytically significant niche within this literature. Di Iulio, Jones, Mahon, and Apperley reported in 2010 the first structurally characterized zinc(II) silsesquioxane complexes, describing their solid-state structures as unprecedented at the time and evaluating the resulting compounds as initiators for the ring-opening polymerization of rac-lactide.20 A structurally distinct approach was taken in our own work on an imine-functionalized POSS ligand, in which the silsesquioxane core and the steric bulk of the imine side arms direct the formation of a tetrazinc complex, denoted Zn4@POSS-1, whose solid-state structure was established by X-ray crystallography alongside an extensive spectroscopic characterization in solution.21 The four zinc centers adopt a distorted tetrahedral geometry, two with a delta and two with a lambda configuration, with Zn-O bond lengths of 1.914(5) to 1.924(4) angstroms and Zn-N bond lengths of 1.979(6) to 2.016(5) angstroms, both ranges comparable to typical Zn(II) Schiff-base complexes, while the silicon-oxygen-silicon angles within the POSS core widen to between 139.6(3) and 167.3(3) degrees at the corners capped by the zinc centers. Zn4@POSS-1 is also structurally distinctive within the broader body of work surveyed in this review. In most of the crystallographically confirmed complexes discussed above, from the copper, manganese, and iron cages to the nickel cylinder and the lanthanide and actinide clusters, the metal centers are encapsulated inside a closed cage, sandwiched between two silsesquioxane ligand planes or embedded within a bridging oxo core sitting at the heart of the assembly. Zn4@POSS-1 departs from this pattern: the four zinc centers are held on the outside of an open, partially condensed POSS scaffold, each capped by one arm of the imine-functionalized ligand rather than being enclosed within a fully closed double-decker or sandwich core. This places Zn4@POSS-1 closer in spirit to the corner-capping assembly mode described for the main-group and alkaline-earth derivatives later in this review, in which a metal center caps an open corner of the cage from the outside, than to the encapsulated, internally templated architectures that dominate the transition-metal and lanthanide chemistry surveyed elsewhere in this article. This complex proved effective as a multisite catalyst for the cycloaddition of CO2 with epoxides to form cyclic carbonates under low CO2 pressure, a transformation of considerable interest for carbon utilization chemistry, and it illustrates how the same coordination chemistry that produces striking copper and manganese cages can be redirected toward small-molecule catalysis when a redox-inactive metal such as zinc is used instead. With styrene oxide as the model substrate, tetrabutylammonium iodide as co-catalyst, and 1 atmosphere of CO2 at 100 degrees Celsius, the catalyst alone was inactive, but the Zn4@POSS-1/TBAI pair reached 96 percent conversion to styrene carbonate at a turnover frequency of 25 per hour, rising to 98 percent conversion at 130 degrees Celsius, and it retained a useful 95 percent conversion even at a ten-fold lower catalyst loading when the reaction time was extended.21

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Figure 4. X-ray crystal structure of Zn4@POSS-1 from Janeta, Lis, Szafert, Chem. Eur. J. 2020, 26, 13686-13697 (ref. 21), rendered directly from the deposited crystal structure (CCDC 1504223). The imine-functionalized POSS core is capped by four Zn(II) centers, each chelated by an N,N-imine side arm in the meso-(delta,delta,lambda,lambda) configuration described in the text.

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Lanthanide and Actinide Metallasilsesquioxanes: Magnetism and Luminescence

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Lanthanide-based metallasilsesquioxanes form a comparatively young but fast-moving subfield, motivated by the combination of structural novelty with magnetic and luminescent function. The first CeIV metallasilsesquioxane complex, reported by Gun'ko, Reilly, Edelmann, and Schmidt in 2001, established that even a large, high-valent lanthanide ion could be accommodated within a silsesquioxane coordination environment.22 Lorenz and coworkers subsequently reported an erbium complex in which two silsesquioxane cages become coupled through a bridging siloxy unit, a transformation that had not previously been observed for a lanthanide-templated system.23 Since 2020, a series of tetranuclear cage-like lanthanide silsesquioxanes built around a prism-like Ln4 core has produced some of the most functionally interesting examples in the entire field. Terbium and europium derivatives display the first luminescence reported for a cage-like lanthanide silsesquioxane, and one terbium-based cage additionally exhibits a magnetic spin-flip transition.24

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Figure 5. X-ray crystal structure of the mixed-lanthanide cage anion of (Et4N)2[(PhSiO1.5)8(Y0.75Dy0.25O1.5)4(O)(NO3)6(EtOH)2(MeCN)2], compound 1 of Kulakova et al., Eur. J. Inorg. Chem. 2021, 2696-2701 (ref. 26), CCDC 2062487, rendered directly from the deposited crystallographic coordinates. Two parallel tetraphenylcyclotetrasiloxanolate macrocycles sandwich a distorted-square (Y0.75Dy0.25O1.5)4 core (left). The tetraethylammonium counter-cation is shown alongside the cage in the side view (right). This is the compound that displays field-induced single-molecule magnet behavior in addition to the characteristic dysprosium green-yellow emission.

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Figure 6. X-ray crystal structure of the homometallic cage anion of (Ph4P)2[(PhSiO1.5)8(DyO1.5)4(O)(NO3)6(EtOH)2(MeCN)2], compound 3 of Kulakova et al., Eur. J. Inorg. Chem. 2021, 2696-2701 (ref. 26), CCDC 2002355, rendered directly from the deposited crystallographic coordinates. The same prism-like topology as in Figure 5 is retained with four Dy(III) centers in the core (left). The tetraphenylphosphonium counter-cation is shown alongside the cage (right). Unlike the mixed Y/Dy analogue, this all-dysprosium cage and its tetraethylammonium salt (compound 2, CCDC 2002354, not shown) do not display slow relaxation of the magnetization, a difference attributed to magnetic interactions between the four Dy(III) centers.

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Related dysprosium and yttrium/dysprosium cages combine field-induced single-molecule magnet behavior with green-yellow emission, yielding the first bifunctional magneto-luminescent silsesquioxane reported in the literature, while mixed terbium/europium cages have been developed specifically as luminescent thermometers operating between 41 and 100 degrees Celsius through a temperature-dependent energy transfer between the two lanthanide centers.25,26 A further mixed-lanthanide series combining dysprosium, europium, terbium, and yttrium in various ratios extends this dual functionality: the dysprosium/europium member behaves as a field-induced single-molecule magnet, with an effective energy barrier of 11.3 wavenumbers under an applied direct-current field, while simultaneously operating as a europium-based emissive thermometer across the range of 293 to 373 kelvin, reaching a maximum relative thermal sensitivity of 1.15 percent per kelvin at 293 kelvin, whereas the terbium- and yttrium-containing congeners of the same series show neither slow magnetic relaxation nor temperature-dependent emission.27 At still higher nuclearity, a tridecanuclear gadolinium(III) cluster with an unprecedented body-centered cuboctahedron core represents the highest nuclearity yet reported for a lanthanide silsesquioxane and was synthesized specifically to explore cryogenic magnetic refrigeration, reaching a maximum magnetic entropy change of 20 joules per kilogram per kelvin at 2 kelvin under an applied field of 7.0 tesla.28 Actinide chemistry entered this field only recently, with Tricoire, Mazzanti, and coworkers reporting in 2024 the first trinuclear uranium(III) metallasilsesquioxane, a complex that exhibits magnetic exchange between the three uranium centers and promotes the reduction of dinitrogen in the presence of a reducing agent, with U-O bond lengths ranging from 2.125(16) to 2.568(17) angstroms and an average value of 2.36(2) angstroms.29

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Figure 7. X-ray crystal structure of the first trinuclear U(III) metallasilsesquioxane, [U3(iBuPOSS)3], of Tricoire et al., Chem. Commun. 2024, 60, 55-58 (ref. 29), rendered directly from the deposited crystallographic coordinates. The three uranium centers (U1, U2, U3) are arranged in a triangular U3(mu-O)6 core, each capped by one iBuPOSS ligand and linked to its neighbors by bridging siloxide oxygens, with U-O distances ranging from 2.125(16) to 2.568(17) angstroms and an average value of 2.36(2) angstroms, consistent with previously reported U(III) siloxide complexes.

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Main-Group and Alkaline-Earth Derivatives

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A smaller number of structurally confirmed metal-POSS complexes involve main-group or alkaline-earth elements rather than transition metals or f-block ions. Duchateau and coworkers prepared a family of tin-containing polyhedral oligometallasilsesquioxanes in 2004 starting from cyclopentyl-substituted silsesquioxane trisilanols. Protonolysis with a tin(II) amide gave three-coordinate Sn(II) dimers of the type [(cyclopentyl)7Si7O11(OX)Sn]2 (compound 2 shown below), which proved hydrolytically unstable and feature a planar, strained (SnO)2 four-membered ring with an O-Sn-O angle of 75.39(13) degrees and an Sn-O-Sn angle of 104.61(13) degrees, the bridging tin-oxygen bonds of 2.177(3) and 2.172(3) angstroms being noticeably longer than the terminal, sigma-bonded tin-oxygen bond of 1.995(3) angstroms, whereas reaction with Cl2Sn(acac)2 gave hydrolytically robust, octahedrally coordinated Sn(IV) mono-tin complexes. Slow hydrolysis of the corresponding tin(IV) chloride cluster instead produced an unprecedented anionic trimeric cluster (compound 6) in which three octahedral Sn(IV) centers are held together by three silsesquioxane cages and four bridging hydroxyl groups, three of them bridging two tin atoms and one bridging all three, with a triethylammonium counterion occupying the remaining corner of the resulting incomplete cube. In this cluster the average tin-oxygen-tin angle at the doubly bridging hydroxyls, 112.3(3) degrees, is noticeably wider than the corresponding angle at the triply bridging hydroxyl, 100.9(3) degrees, while the tin atoms are linked to the silsesquioxane cages by tin-oxygen-silicon bonds averaging 1.974(4) angstroms in length, with a tin-oxygen-silicon angle of about 140 degrees at the monodentate silsesquioxane linkages and about 134 degrees at the bidentate ones. Despite this structural sophistication, none of the tin(IV) complexes showed any catalytic activity when screened in the Baeyer-Villiger oxidation of cyclohexanone, the Oppenauer oxidation of isopropanol, or the epoxidation of cyclooctene, a result the authors attributed to the coordinative saturation and reduced Lewis acidity of the octahedral, and in one case anionic, tin centers.30

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Figure 8. Left: the anionic trinuclear Sn(IV) cluster {[(cyclopentyl)7Si7O12Sn]3(mu2-OH)3(mu3-OH)}-{HNEt3}+ (compound 6, CCDC 238581). Right: the three-coordinate Sn(II) dimer [(cyclopentyl)7Si7O11(OSiMe3)Sn]2 (compound 2, CCDC 238582), with a center of inversion in the planar (SnO)2 ring. Both structures from Duchateau et al., Dalton Trans. 2004, 2677-2682 (ref. 30), rendered directly from the deposited crystallographic coordinates.

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Lorenz, Blaurock, and Edelmann reported in the same period the first metallasilsesquioxane derivative of a heavier alkaline-earth metal, a dinuclear calcium complex in which two anionic silsesquioxane cages bridge a pair of unsymmetrically solvated calcium centers.31 Although these examples remain fewer in number than their transition metal and lanthanide counterparts, they demonstrate that the silsesquioxane cage can stabilize an unusually broad span of ionic radii and electronic configurations, from small trivalent tin to large, weakly coordinating alkaline-earth cations.

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Copper Cage Silsesquioxanes: The Dominant Family

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Copper accounts for the largest and most rapidly growing body of crystallographically confirmed metal-POSS chemistry, driven principally by the systematic work of Bilyachenko and coworkers. Across this family the recurring synthetic purpose was catalytic rather than purely structural, since nearly every reported cage was subsequently tested as a precatalyst for the peroxidative oxidation of light alkanes, cyclic hydrocarbons, and secondary alcohols with hydrogen peroxide or tert-butyl hydroperoxide, and crystallographic confirmation of the cage architecture was pursued specifically because catalytic performance was found to depend on the precise nuclearity and connectivity of the metal-oxo core rather than on solution composition alone.2,3,4,6,7,8,9,10,11,13

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The binuclear \"cooling tower\" complex [(PhSiO1.5)10(CuO)2(NaO0.5)2] reported in 2013 established the basic architecture of a copper-silsesquioxane cage, in which cyclic phenylsilsesquioxane ligands sandwich a small metal-oxo core, and its structure was confirmed by single-crystal X-ray diffraction, with copper-oxygen bond lengths of 1.906(3) to 1.956(4) angstroms and a silicon-oxygen-silicon bridging angle as wide as 166.2(3) degrees.2 The complex was synthesized specifically to probe alkane and alcohol oxidation catalysis, and in benzene oxidation with hydrogen peroxide and nitric acid as promoter it reached a turnover number of 550 and a product yield of up to 41 percent, while oxidation of 1-phenylethanol to acetophenone with tert-butyl hydroperoxide proceeded in a yield approaching 100 percent after four hours.

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Nonanuclear methylsilsesquioxane cages appeared in 2017, alongside trinuclear and hexanuclear congeners obtained from the same reaction system, each nuclearity and connectivity again established by diffraction, with mean copper-copper and copper-oxygen siloxanolate distances of 2.869(5) and 1.935(9) angstroms in the trinuclear cage.3 These complexes were likewise developed as alkane and alcohol oxidation catalysts, and the trinuclear cage converted 1-phenylethanol to acetophenone in 96 percent yield and cyclohexanol to cyclohexanone in 77 percent yield, while cyclohexane oxidation with hydrogen peroxide reached a total yield of 20 percent and a turnover number of 184, several times higher than the yield obtained with simple copper nitrate under the same conditions.

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A distinct nonanuclear phenylsilsesquioxane cage of Cu9Na6 composition, formed with the assistance of a phenanthroline ligand that does not itself enter the final structure, followed in 2018, together with an ionic Cu9Na4 congener obtained under related conditions.4 Both complexes were prepared as catalysts for the oxidative amidation of benzyl alcohol, a reaction in which the Cu9Na6 cage required only 100 parts per million of copper and reached a turnover number of 7700 and a turnover frequency of 325 per hour, substantially outperforming copper oxide alone under the same conditions, and it additionally converted cyclohexanone or acetophenone in 63 or 98 percent yield in alcohol oxidation with tert-butyl hydroperoxide.

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The coordinating role of the alkali metal cation proved to be a recurring structural variable rather than an incidental detail. Sandwich-like Cu4M2 complexes built around lithium, sodium, and potassium templates, distinguished crystallographically by intramolecular alkali metal to alkali metal separations ranging from 10.35 to 11.45 angstroms, were shown to direct the assembly toward distinct architectures even when the silsesquioxane and transition metal components were otherwise unchanged, although specific catalytic yields for this particular series were not reported in the accessible source text.5 The corresponding rubidium and cesium templated tetracopper cages, resolved crystallographically with rubidium to rubidium separations as long as 9.39 angstroms, were tested extensively as alkane oxidation and carboxylation catalysts, reaching a 35 percent yield and a turnover number of 320 in cyclohexane oxidation with hydrogen peroxide and a 50 percent total yield with a turnover number of 277 in the oxidative carboxylation of n-butane to a mixture of pentanoic acids, in addition to alcohol oxidations that converted 1-phenylethanol to acetophenone in 98 percent yield.6

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Heptanuclear cages bridged additionally by benzoate ligands were reported between 2019 and 2021, with the three linearly disposed copper centers in the cage subtending an angle of 178.04(2) degrees.7 The heptanuclear complex was again evaluated as an alkane and alcohol oxidation catalyst, converting cyclohexane to a combined yield of 32 percent of alcohol and ketone with a turnover number of 290 within two hours, a result that compared favorably with a copper-sodium silsesquioxane analog tested under the same conditions, and it oxidized the acetophenone precursor 1-phenylethanol with tert-butyl hydroperoxide in 90 percent yield and a turnover number of 900.

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Tetranuclear complexes obtained through the oxidative cleavage of a bis(phosphine) ligand, in this case 1,1-bis(diphenylphosphino)methane, were reported in 2019 as a palanquin-like Cu4Na4 cage in which the shortest distance between opposing silicon atoms of the silsesquioxane ligand measured 5.114 angstroms.8 This complex converted cyclohexane to cyclohexanol in 26 percent yield with a turnover number of 240 and an activation energy of 13.6 kilocalories per mole, and it oxidized 1-phenylethanol to acetophenone in essentially quantitative yield.

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Heterometallic Cu4/M4 architectures further diversified the structural landscape reported between 2019 and 2023. A series of eight cesium and rubidium templated Cu4M4 coordination polymers, in which the centers of neighboring cages were separated by 13.97 angstroms in the solid state, were developed for the hydrocarboxylation of cycloalkanes, converting cyclohexane to cyclohexanecarboxylic acid in up to 37.8 percent yield and cyclopentane to the corresponding acid in 26.4 percent yield, in addition to reaching a 45 percent yield in direct cyclohexane oxidation with hydrogen peroxide.9 A related cage-like Cu5Cs4 phenylsilsesquioxane, with cesium to cesium separations of 9.54 and 11.62 angstroms, was instead developed for the Baeyer-Villiger oxidation of cyclohexanone to epsilon-caprolactone with meta-chloroperoxybenzoic acid, reaching a quantitative yield and a turnover number of 250 under microwave irradiation, and it additionally supported a tandem route directly from cyclohexane to the lactone in 17 percent yield, together with alcohol oxidations reaching 90 percent yield in the conversion of 1-phenylethanol to acetophenone.10

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The record for nuclearity in this family has continued to rise, from a Cu12 cage decorated with additional Cu(I) phosphine moieties in 2024, whose copper-copper-copper trimer units are significantly distorted with angles of 140.70 and 141.77 degrees, to a Cu13Na2 cage assembled with the assistance of acetate ligands in 2025, the latter structure solved using synchrotron radiation.11,12 The Cu12 complex proved to be an active catalyst for both the peroxidative oxidation and the oxidative carboxylation of C2 to C4 alkanes, reaching a turnover number of up to 534 in propane oxidation and a 50 percent combined yield of pivalic and isovaleric acids in the carboxylation of isobutane, and it oxidized 1-phenylethanol to acetophenone in 96 percent yield with a turnover number of 960. The Cu13Na2 cage itself was tested as a precatalyst in the Baeyer-Villiger oxidation of cyclohexanone, reaching essentially quantitative yields of epsilon-caprolactone with meta-chloroperoxybenzoic acid as oxidant, and it also supported a direct tandem route from cyclohexane to the same lactone in 25 to 26 percent yield, a modest but meaningful improvement over the heptanuclear Cu7-benzoate congener from the same group on this more demanding substrate.12

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An octanuclear Cu8 complex bearing 3-phenyl-5-(2-pyridyl)pyrazolate ligands, in which two zigzag Cu4 tetramers are sandwiched by two cyclic pentameric silsesquioxane ligands with a longest intramolecular copper to copper separation of 11.08 angstroms, was likewise synthesized as an alkane oxidation catalyst, converting n-heptane to a 14 percent yield of oxidation products and methylcyclohexane to a 15 percent yield under comparable conditions with hydrogen peroxide and nitric acid as promoter.13

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\n\"X-ray\n\"X-ray\n
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Figure 9. X-ray crystal structure of the record-nuclearity Cu13Na2 cage of Bilyachenko et al., Chem. Eur. J. 2025, 31, e202403604 (ref. 12), rendered directly from the deposited crystallographic coordinates. The left view shows the fused copper-siloxanolate core, with the crystallographically independent Cu1 and Cu2 centers and their symmetry-related counterparts (Cu3, Cu4 and primed equivalents) bridged by phenylsiloxanolate oxygens. The right view, rotated to look down the pseudo-macrocyclic axis, shows how the copper centers are threaded through the large siloxanolate ring formed by the ligand framework. Acetate ligands and the two bridging sodium centers that complete the Cu13Na2 formulation lie above and below this copper-rich core and are omitted here for clarity.

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What Crystallography Reveals: Emerging Structural Trends

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Several patterns recur across this body of crystallographic work regardless of which metal is involved. The alkali metal cation present during self-assembly, whether lithium, sodium, potassium, rubidium, or cesium, is rarely a passive spectator. Its ionic radius consistently governs whether the silsesquioxane ligand adopts a cyclic or acyclic conformation and whether the resulting cage is neutral, cationic, or anionic, a relationship documented independently for copper, manganese, and iron systems. A second recurring theme is the steady increase in reported nuclearity over time within the copper family in particular, from the two-copper cooling tower of 2013 to cages containing twelve or thirteen copper centers within the past two years, a trend that appears to reflect refinements in self-assembly conditions and the increasing use of synchrotron radiation to solve structures that would otherwise diffract poorly. Finally, the correlation between confirmed cage topology and function, whether catalytic activity in oxidation chemistry, single-molecule magnet behavior, or luminescence thermometry, illustrates why single-crystal X-ray diffraction remains indispensable in this field rather than a merely confirmatory afterthought. Spectroscopic and computational methods can propose a plausible structure, but only diffraction data have consistently distinguished between the closely related cage topologies that give rise to markedly different physical and chemical properties.

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Conclusions and Outlook

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The metal-POSS complexes surveyed here span nearly the entire periodic table, from copper cages of steadily increasing nuclearity to the first actinide example reported only in 2024, and in every case single-crystal X-ray diffraction has been the method that transformed a plausible formula into a confirmed molecular structure. The copper family in particular continues to grow at a pace that suggests further records in nuclearity are likely within the next few years, while the lanthanide and actinide subfields remain comparatively open for structural discovery. For a research program centered on zinc Schiff base and imine-functionalized POSS chemistry, the comparative view offered by this survey suggests that the alkali metal template effect documented so thoroughly for copper, manganese, and iron systems may offer an underexplored strategy for directing the nuclearity and topology of future zinc-based cages as well.

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","doi":"https://doi.org/10.59350/8e62f-05m22","guid":"tag:blogger.com,1999:blog-2875892712213933214.post-7230213059130383354","image":"https://blogger.googleusercontent.com/img/a/AVvXsEgbtkRdpRYiO2JHyQ1SnSxcpdDJhpJDd_a5auAqpTWOOL0NnM45ib0cA18ej-HckPJmc315dogMruGHs6Ao2P27QWrzlbAkY5GiffVrXTuWoGxtbeNEcUKo8iqDnMma_icTxMgnDrDNbFLere6HAUbZkyhjgiAzEHxnUvOffUijinsjhoJHsgPhsM0MbhE=s72-c","language":"en","license":"https://creativecommons.org/licenses/by/4.0/legalcode","published_at":1788998400,"reference":[{"id":"https://doi.org/10.1016/0277-5387(95)85009-0","unstructured":"Feher, F. J., & Budzichowski, T. A. (1995). Silasesquioxanes as ligands in inorganic and organometallic chemistry. Polyhedron, 14(22), 3239\u20133253."},{"id":"https://doi.org/10.1002/ejic.201300878","unstructured":"Bilyachenko, A. N., Dronova, M. S., Yalymov, A. I., Korlyukov, A. A., Shul'pina, L. S., Arkhipov, D. E., Shubina, E. S., Levitsky, M. M., Kirilin, A. D., & Shul'pin, G. B. (2013). Binuclear Cage\u2010Like Copper(II) Silsesquioxane (\"Cooling Tower\") \u2013 Its High Catalytic Activity in the Oxidation of Benzene and Alcohols. European Journal of Inorganic Chemistry, 2013(30), 5240\u20135246."},{"id":"https://doi.org/10.1021/acs.inorgchem.7b00061","unstructured":"Bilyachenko, A. N., Kulakova, A. N., Levitsky, M. M., Petrov, A. A., Korlyukov, A. A., Shul'pina, L. S., Khrustalev, V. N., Dorovatovskii, P. V., Vologzhanina, A. V., Tsareva, U. S., Golub, I. E., Gulyaeva, E. S., Shubina, E. S., & Shul'pin, G. B. (2017). Unusual Tri-, Hexa-, and Nonanuclear Cu(II) Cage Methylsilsesquioxanes: Synthesis, Structures, and Catalytic Activity in Oxidations with Peroxides. Inorganic Chemistry, 56(7), 4093\u20134103."},{"id":"https://doi.org/10.1021/acs.inorgchem.8b01496","unstructured":"Astakhov, G. S., Bilyachenko, A. N., Korlyukov, A. A., Levitsky, M. M., Shul'pina, L. S., Bantreil, X., Lamaty, F., Vologzhanina, A. V., Shubina, E. S., Dorovatovskii, P. V., Nesterov, D. S., Pombeiro, A. J. L., & Shul'pin, G. B. (2018). High-Cluster (Cu9) Cage Silsesquioxanes: Synthesis, Structure, and Catalytic Activity. Inorganic Chemistry, 57(18), 11524\u201311529."},{"id":"https://doi.org/10.3390/molecules27196205","unstructured":"Bilyachenko, A. N., Khrustalev, V. N., Zueva, A. Y., Titova, E. M., Astakhov, G. S., Zubavichus, Y. V., Dorovatovskii, P. V., Korlyukov, A. A., Shul'pina, L. S., Shubina, E. S., Kozlov, Y. N., Ikonnikov, N. S., Gelman, D., & Shul'pin, G. B. (2022). A Novel Family of Cage-like (CuLi, CuNa, CuK)-phenylsilsesquioxane Complexes with 8-Hydroxyquinoline Ligands: Synthesis, Structure, and Catalytic Activity. Molecules, 27(19), 6205."},{"id":"https://doi.org/10.1021/acs.organomet.2c00649","unstructured":"Bilyachenko, A. N., Khrustalev, V. N., Astakhov, G. S., Zueva, A. Y., Arteev, I. S., Zubavichus, Y. V., Korlyukov, A. A., Dorovatovskii, P. V., Shul'pina, L. S., Ikonnikov, N. S., Kirillova, M. V., Shubina, E. S., Kozlov, Y. N., Kirillov, A. M., & Shul'pin, G. B. (2023). Cagelike Rb2-, K2-, and Na2-Tetracopper(II) Silsesquioxanes with Quaternary Ammonium Cations: Synthesis, Structures, and Catalytic Activity. Organometallics, 42(18), 2577\u20132589."},{"id":"https://doi.org/10.3390/molecules27238505","unstructured":"Bilyachenko, A. N., Khrustalev, V. N., Gutsul, E. I., Zueva, A. Y., Korlyukov, A. A., Shul'pina, L. S., Ikonnikov, N. S., Dorovatovskii, P. V., Gelman, D., Shubina, E. S., & Shul'pin, G. B. (2022). Hybrid Silsesquioxane/Benzoate Cu7-Complexes: Synthesis, Unique Cage Structure, and Catalytic Activity. Molecules, 27(23), 8505."},{"id":"https://doi.org/10.3390/catal9020154","unstructured":"Kulakova, A. N., Khrustalev, V. N., Zubavichus, Y. V., Shul'pina, L. S., Shubina, E. S., Levitsky, M. M., Ikonnikov, N. S., Bilyachenko, A. N., Kozlov, Y. N., & Shul'pin, G. B. (2019). Palanquin-Like Cu4Na4 Silsesquioxane Synthesis (via Oxidation of 1,1-bis(Diphenylphosphino)methane), Structure and Catalytic Activity in Alkane or Alcohol Oxidation with Peroxides. Catalysts, 9(2), 154."},{"id":"https://doi.org/10.1021/acs.cgd.1c01225","unstructured":"Bilyachenko, A. N., Astakhov, G. S., Kulakova, A. N., Korlyukov, A. A., Zubavichus, Y. V., Dorovatovskii, P. V., Shul'pina, L. S., Shubina, E. S., Ikonnikov, N. S., Kirillova, M. V., Zueva, A. Y., Kirillov, A. M., & Shul'pin, G. B. (2022). Exploring Cagelike Silsesquioxane Building Blocks for the Design of Heterometallic Cu4/M4Architectures. Crystal Growth & Design, 22(4), 2146\u20132157."},{"id":"https://doi.org/10.1021/acs.inorgchem.3c01989","unstructured":"Bilyachenko, A. N., Arteev, I. S., Khrustalev, V. N., Shul'pina, L. S., Korlyukov, A. A., Ikonnikov, N. S., Shubina, E. S., Kozlov, Y. N., Reis Concei\u00e7\u00e3o, N., Guedes da Silva, M. F. C., Mahmudov, K. T., & Pombeiro, A. J. L. (2023). Cage-like Cu5Cs4-Phenylsilsesquioxanes: Synthesis, Supramolecular Structures, and Catalytic Activity. Inorganic Chemistry, 62(33), 13573\u201313586."},{"id":"https://doi.org/10.1021/acs.inorgchem.4c02806","unstructured":"Bilyachenko, A. N., Khrustalev, V. N., Arteev, I. S., Shul'pina, L. S., Ikonnikov, N. S., Kirillova, M. V., Shubina, E. S., Kirillov, A. M., Kozlov, Y. N., Lobanov, N. N., Ragimov, K. G., & Sun, D. (2024). Cu12-Methylsilsesquioxane Cage Decorated with Cu(dppe)2 Moieties for Mild Oxidative Functionalization of Alkanes. Inorganic Chemistry, 63(43), 20404\u201320414."},{"id":"https://doi.org/10.1002/chem.202403604","unstructured":"Bilyachenko, A. N., Khrustalev, V. N., Huang, Z., Dorovatovskii, P. V., Shubina, E. S., Lobanov, N. N., Wang, Z., Ragimov, K., Reis Concei\u00e7\u00e3o, N., Mahmoud, A. G., & Pombeiro, A. J. L. (2024). Combination of Phenylsilsesquioxane and Acetate Ligands as an Approach to a Record High Nuclear Cu13Na2\u2010Cage. Synthesis, Unique Structure, and Catalytic Activity. Chemistry \u2013 A European Journal, 31(5)."},{"id":"https://doi.org/10.1039/d4dt02690j","unstructured":"Bilyachenko, A. N., Khrustalev, V. N., Huang, Z., Shul'pina, L. S., Dorovatovskii, P. V., Shubina, E. S., Ikonnikov, N. S., Lobanov, N. N., Ragimov, K., & Sun, D. (2024). An octanuclear 3-phenyl-5-(2-pyridyl)pyrazolate/phenylsilsesquioxane complex: synthesis, unique structure, and catalytic activity. Dalton Transactions, 53(48), 19102\u201319106."},{"id":"https://doi.org/10.3390/molecules21050665","unstructured":"Bilyachenko, A., Yalymov, A., Shul'pina, L., Mandelli, D., Korlyukov, A., Vologzhanina, A., Es'kova, M., Shubina, E., Levitsky, M., & Shul'pin, G. (2016). Novel Cage-Like Hexanuclear Nickel(II) Silsesquioxane. Synthesis, Structure, and Catalytic Activity in Oxidations with Peroxides. Molecules, 21(5), 665."},{"id":"https://doi.org/10.1002/zaac.200800292","unstructured":"Lorenz, V., Blaurock, S., & Edelmann, F. T. (2008). The First Heterobimetallic Metallasilsesquioxane Derivatives of Manganese. Zeitschrift F\u00fcr Anorganische Und Allgemeine Chemie, 634(15), 2819\u20132824."},{"id":"https://doi.org/10.1039/d2qi01054b","unstructured":"Astakhov, G. S., Khrustalev, V. N., Dronova, M. S., Gutsul, E. I., Korlyukov, A. A., Gelman, D., Zubavichus, Y. V., Novichkov, D. A., Trigub, A. L., Shubina, E. S., & Bilyachenko, A. N. (2022). Cage-like manganesesilsesquioxanes: features of their synthesis, unique structure, and catalytic activity in oxidative amidations. Inorganic Chemistry Frontiers, 9(17), 4525\u20134537."},{"id":"https://doi.org/10.1021/acs.inorgchem.3c02040","unstructured":"Bilyachenko, A. N., Gutsul, E. I., Khrustalev, V. N., Chusova, O., Dorovatovskii, P. V., Aliyeva, V. A., Paninho, A. B., Nunes, A. V. M., Mahmudov, K. T., Shubina, E. S., & Pombeiro, A. J. L. (2023). A Family of Cagelike Mn-Silsesquioxane/Bathophenanthroline Complexes: Synthesis, Structure, and Catalytic and Antifungal Activity. Inorganic Chemistry, 62(38), 15537\u201315549."},{"id":"https://doi.org/10.1021/acs.inorgchem.3c03587","unstructured":"Bilyachenko, A. N., Khrustalev, V. N., Dorovatovskii, P. V., Shul'pina, L. S., Ikonnikov, N. S., Shubina, E. S., Lobanov, N. N., Aliyeva, V. A., Nunes, A. V. M., Mahmudov, K. T., Kozlov, Y. N., & Pombeiro, A. J. L. (2024). Fe(III)-Based Phenylsilsesquioxane/Acetylacetonate Complexes: Synthesis, Cage-like Structure, and High Catalytic Activity. Inorganic Chemistry, 63(4), 1909\u20131918."},{"id":"https://doi.org/10.1021/acs.inorgchem.4c01748","unstructured":"Shen, Q., Sheng, K., Gao, Z.-Y., Bilyachenko, A., Huang, X.-Q., Azam, M., Tung, C.-H., & Sun, D. (2024). Vanadium-Silsesquioxane Nanocages as Heterogeneous Catalysts for Synthesis of Quinazolinones. Inorganic Chemistry, 63(28), 13022\u201313030."},{"id":"https://doi.org/10.1021/ic101809r","unstructured":"Di Iulio, C., Jones, M. D., Mahon, M. F., & Apperley, D. C. (2010). Zinc(II) Silsesquioxane Complexes and Their Application for the Ring-Opening Polymerization of rac-Lactide. Inorganic Chemistry, 49(22), 10232\u201310234."},{"id":"https://doi.org/10.1002/chem.202002996","unstructured":"Janeta, M., Lis, T., & Szafert, S. (2020). Zinc Imine Polyhedral Oligomeric Silsesquioxane as a Quattro\u2010Site Catalyst for the Synthesis of Cyclic Carbonates from Epoxides and Low\u2010Pressure CO2. Chemistry \u2013 A European Journal, 26(60), 13686\u201313697."},{"id":"https://doi.org/10.1002/1521-3773(20010401)40:7%3c1279::aid-anie1279%3e3.0.co;2-2","unstructured":"Gun'ko, Y. K., Reilly, R., Edelmann, F. T., & Schmidt, H.-G. (2001). The First CeIV Metallasilsesquioxane Complex: [Ce{(c-C6H11)8Si8O13}2(py)3]. Angewandte Chemie International Edition, 40(7), 1279\u20131281. https://doi.org/10.1002/1521-3773(20010401)40:7%3c1279::aid-anie1279%3e3.0.co;2-2"},{"id":"https://doi.org/10.1002/ejic.201000186","unstructured":"Lorenz, V., Blaurock, S., Hrib, C. G., & Edelmann, F. T. (2010). Coupling of Silsesquioxane Cages in the Coordination Sphere of Erbium. European Journal of Inorganic Chemistry, 2010(18), 2605\u20132608."},{"id":"https://doi.org/10.1002/chem.202003351","unstructured":"Kulakova, A. N., Bilyachenko, A. N., Levitsky, M. M., Khrustalev, V. N., Shubina, E. S., Felix, G., Mamontova, E., Long, J., Guari, Y., & Larionova, J. (2020). New Luminescent Tetranuclear Lanthanide\u2010Based Silsesquioxane Cage\u2010Like Architectures. Chemistry \u2013 A European Journal, 26(70), 16594\u201316598."},{"id":"https://doi.org/10.1002/ejic.202100308","unstructured":"Kulakova, A. N., Nigoghossian, K., F\u00e9lix, G., Khrustalev, V. N., Shubina, E. S., Long, J., Guari, Y., Carlos, L. D., Bilyachenko, A. N., & Larionova, J. (2021). New Magnetic and Luminescent Dy(III) and Dy(III)/Y(III) Based Tetranuclear Silsesquioxane Cages. European Journal of Inorganic Chemistry, 2021(27), 2696\u20132701."},{"id":"https://doi.org/10.1039/d3ra04901a","unstructured":"F\u00e9lix, G., Sene, S., Kulakova, A., Bilyachenko, A. N., Khrustalev, V. N., Shubina, E. S., Guari, Y., & Larionova, J. (2023). Tetranuclear lanthanide-based silsesquioxanes: towards a combination of a slow relaxation of the magnetization and a luminescent thermometry. RSC Advances, 13(37), 26302\u201326312."},{"id":"https://doi.org/10.1016/j.chphma.2022.04.008","unstructured":"Sheng, K., Wang, R., Bilyachenko, A., Khrustalev, V., Jagodi\u010d, M., Jagli\u010di\u0107, Z., Li, Z., Wang, L., Tung, C., & Sun, D. (2022). Tridecanuclear Gd(III)-silsesquioxane: Synthesis, structure, and magnetic property. ChemPhysMater, 1(4), 247\u2013251."},{"id":"https://doi.org/10.1039/d3cc05390c","unstructured":"Tricoire, M., Jori, N., Fadaei Tirani, F., Scopelliti, R., Z\u0306ivkovi\u0107, I., Natrajan, L. S., & Mazzanti, M. (2024). A trinuclear metallasilsesquioxane of uranium(iii). Chemical Communications, 60(1), 55\u201358."},{"id":"https://doi.org/10.1039/b407471h","unstructured":"Duchateau, R., Dijkstra, T. W., Severn, J. R., van Santen, R. A., & Korobkov, I. V. (2004). Synthesis and characterization of tin containing polyhedral oligometallasilsesquioxanes (POMSS). Dalton Transactions, (17), 2677."},{"id":"https://doi.org/10.1002/zaac.200700370","unstructured":"Lorenz, V., Blaurock, S., & Edelmann, F. T. (2008). [{\u03bc\u2010Cy8Si8O13}2Ca(DME)Ca(THF)2] \u2013 The First Metallasilsesquioxane Derivative of a Heavier Alkaline Earth Metal. Zeitschrift F\u00fcr Anorganische Und Allgemeine Chemie, 634(3), 441\u2013444."}],"rid":"cgwz4-t1w67","summary":"Polyhedral oligomeric silsesquioxanes (POSS) have long served as more than a hybrid organic-inorganic filler for polymers. Their partially condensed silanol forms present a rigid, oxygen-rich pocket that closely resembles a fragment of amorphous silica, and this pocket is an excellent ligand for metal ions of nearly every part of the periodic table.","tags":["Catalysis","Metal-POSS Complexes","POSS","Silsesquioxane","X-ray Crystallography"],"title":"Crystallographically Confirmed Metal-POSS Complexes","updated_at":1789111820,"url":"https://silsesquioxane.blogspot.com/2026/09/crystallographically-confirmed-metal.html","version":"v1"},{"authors":[{"contributor_roles":[],"name":"The WiNoDa-Team"}],"blog":{"authors":null,"community_id":"d21c5e78-88bc-432c-a20b-4e8a8ead1693","created":1752796800,"current_feed_url":null,"description":"Wissenslabor f\u00fcr naturwissenschaftliche Sammlungen und objektzentrierte Daten","doi":"https://doi.org/10.59350/winoda","favicon":"https://rogue-scholar.org/api/communities/d21c5e78-88bc-432c-a20b-4e8a8ead1693/logo","feed_format":"application/atom+xml","feed_url":"https://winoda.de/feed/atom/","filter":null,"generator":"WordPress","home_page_url":"https://winoda.de","issn":null,"language":"deu","license":"https://creativecommons.org/licenses/by/4.0/legalcode","prefix":"10.59350","relative_url":null,"secure":true,"slug":"winoda","status":"active","subfield":"1209","title":"WiNoDa Knowledge Lab","updated":1789036758,"use_api":false},"blog_name":"WiNoDa Knowledge Lab","blog_slug":"winoda","content_html":"
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Die r\u00e4umliche Anordnung von Proben innerhalb einer Fundstelle kann Muster aufzeigen und Pflanzenreste mit fr\u00fcheren sozialen Praktiken in Verbindung bringen \"\ud83c\udf31\"

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\"Social
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Neugierig, wie das funktioniert? Finden Sie es am 9. Oktober in unserem geostatistischen \"Bring-Your-Data\"-Workshop mit dem Titel \"Pflanzenreste, r\u00e4umliche Erkenntnisse\" heraus, in dem Sie mehr \u00fcber folgende Themen erfahren:

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\"\ud83d\udd39\"R\u00e4umliche Struktur und Variabilit\u00e4t von Daten

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\"\ud83d\udd39\"Experimentelle Variogramme

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\"\ud83d\udd39\"Geostatistische Modelle

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\"\ud83d\udd39\"Durch Kriging erzeugte Vorhersagefl\u00e4chen

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\"\ud83d\udd39\"Arch\u00e4ologische Interpretation r\u00e4umlicher Muster

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Au\u00dferdem haben Sie die M\u00f6glichkeit, Ihre eigenen Daten zum Workshop mitzubringen und Unterst\u00fctzung bei der Aufbereitung f\u00fcr die geplanten Analysen zu erhalten \"\ud83d\udcbb\"

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Egal, ob Sie sich bereits mit Geostatistik auskennen oder einfach nur Lust haben, etwas Neues zu lernen \u2013 Sie sind herzlich eingeladen, dabei zu sein!

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Anmeldungen sind bis zum 25. September 2026 m\u00f6glich.

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Weitere Informationen und Anmeldung auf unserer Website: https://winoda.de/event/byod-de/
","doi":"https://doi.org/10.59350/v3gs5-x9f45","guid":"https://winoda.de/?p=15478","image":"https://winoda.de/wp-content/uploads/2026/08/BYOD.png","language":"de","license":"https://creativecommons.org/licenses/by/4.0/legalcode","published_at":1788998400,"rid":"7kaf8-7f655","summary":"Die r\u00e4umliche Anordnung von Proben innerhalb einer Fundstelle kann Muster aufzeigen und Pflanzenreste mit fr\u00fcheren sozialen Praktiken in Verbindung bringen \ud83c\udf31 Neugierig, wie das funktioniert?","tags":["WiNoDa Knowledge Lab Journal","BYOD","CfP","Datenkompetenz","Tools"],"title":"Call for Participants: Plant Remains, Spatial Gains. Bring-your-data geo-statistical workshop","updated_at":1789111812,"url":"https://winoda.de/2026/09/10/call-for-participants-plant-remains-spatial-gains-bring-your-data-geo-statistical-workshop/","version":"v1"},{"authors":[{"affiliation":[{"id":"https://ror.org/051fd9666","name":"Case Western Reserve University"}],"contributor_roles":[],"family":"McGaugh","given":"Stacy","url":"https://orcid.org/0000-0002-9762-0980"}],"blog":{"authors":null,"community_id":"82262dc6-3666-40e2-939a-d4d637d0fd8f","created":1713312000,"current_feed_url":null,"description":"A Blog About the Science and Sociology of Cosmology and Dark Matter","doi":"https://doi.org/10.59350/tritonstation","favicon":"https://rogue-scholar.org/api/communities/82262dc6-3666-40e2-939a-d4d637d0fd8f/logo","feed_format":"application/atom+xml","feed_url":"https://tritonstation.com/feed/atom/","filter":null,"generator":"WordPress","home_page_url":"https://tritonstation.com","issn":null,"language":"eng","license":"https://creativecommons.org/licenses/by/4.0/legalcode","prefix":"10.59350","relative_url":null,"secure":true,"slug":"tritonstation","status":"active","subfield":"3103","title":"Triton Station","updated":1789075797,"use_api":true},"blog_name":"Triton Station","blog_slug":"tritonstation","content_html":"

I’ve been trying to think more seriously about the entity that set off the LZ experiment. I was dismissive of the possibility of it being dark matter, perhaps unfairly so. On further reflection, I feel only fairly dismissive.

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First, the formal significance that is claimed is 2.6\u03c3. That seems to be a fair and fairly conservative statement. So it seems something did happen, the question is what. The odds of a 2.6\u03c3 event are about 1 in 200, so a fluke seems unlikely.

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I can think of three generic possibilities:

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  1. It’s a fluke.
    2. \n\n\n\n
  2. It’s dark matter (huzzah!)
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  3. It’s some strange new particle-entity that is not dark matter.
    4. \n
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I remain of the opinion that the most likely possibility is that is is a fluke. I know I just said that seems unlikely, but “seems” is doing a lot of work here. I think it is fair to say that known explanations are excluded at this confidence, but that leaves a lot of unknowns. Most unknowns turn out to be boring.

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We’ve been down this road many times. The LHC has been running for many years now. It detected the Higgs particle, which was the last missing piece of the Standard Model. That’s a great success. It was hoped that the LHC would also reveal new physics beyond the Standard Model. That it has not done. But there have been many hints during its operation. These appear as glitches (deviations from expectation); there have been multiple glitches that appeared to be significant at the 2.something \u03c3 level. Each time such a glitch was reported, it resulted in a flurry of theoretical activity. Within days, the arxiv preprint server would be inundated with hundreds (literally hundreds) of preprints staking out a claim as to what the latest glitch might be. Each time more data were acquired, the glitch went away. So this seems like another such occasion, making (1), a fluke, seem like the least improbable outcome.

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This is why the [arbitrary] threshold for discovery is set at 5\u03c3 (1 in 3.5 million). Flukes at the 2.something \u03c3 level happen too easily, too often. This phenomenon is not restricted to particle physics. The same thing happens in astronomy all the time. All the gorram time. It’s almost as if nature places more probability in the tail of the distribution for “weird” events than the Gaussian statistics we use say there should be.

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Given this experience, finding a new particle outside the bounds of the Standard Model of Particle Physics seems a lot less likely than 1 in 200. Seems is again doing a lot of work here. How likely 1 in 200 hundred seems depends on your priors. If you’ve been working on this for a long time in the hopes of a positive result, these odds seem pretty good:

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\"I have been waiting for a positive result for, oh, my god, 40 years. So you can bet I'm very, very excited by the LZ results.\"

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Katy Freese

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If, like me, you’ve already convinced yourself that dark matter cannot explain the kinematic data for galaxies, then it is just another opportunity for the eyes to roll up inside the skull. Obviously we can’t both be right, which is why we do these experiments.

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So what about the other possibilities, (2) and (3)? If the event is real, it is tempting to believe that it is dark matter. That’s what the experiment was designed to detect, after all, so that’s a natural first assumption. But just because you’re looking for something doesn’t guarantee that when you find something you find what you’ve been looking for.

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As I’ve reviewed before, we’re way past the regime of what we expected to find. So it’d be great to find something, but there’s little reason at this point to expect that something to be what we set out to find. So it might be dark matter (2) or it might be something completely different (3). I’ve no way to weigh the odds of those possibilities because they both seem very unlikely.

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For WIMP-like dark matter we at least have some expectations, and this event does not conform to those expectations. It is too high energy. For every event like this one, the detector should have already recorded lots and lots of lower energy events.

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That doesn’t mean it isn’t dark matter (2), just that it isn’t what we expected. But we already missed out on what we were expecting, so maybe? Or maybe it is something unrelated (3), or nothing at all (1). One event does not help override whatever assumption bias we might have had about these possibilities to start.

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To be convincing…

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It occurs to me that I am likely to hold the putative detection of dark matter to a higher standard than other scientists. So what would I find convincing?

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I put the fifth criterion in parentheses because it is a very high bar, and I can conceive of being persuaded to soften it. It is also more advanced tuition than most physicists have contemplated, so let’s start with the more basic requirements.

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At present, none of the above criteria have been met by the new LZ result. There is an old claim to a significant detection by DAMA that satisfies the first criterion but was never independently reproduced, so fails the second criterion. Nobody outside the original experiment takes it seriously now for that reason. It is sobering to realize that while new and exciting, LZ has not yet progressed as far down this list as DAMA.

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Supposing both the first and second requirements are met, then we have a new particle. That is certainly interesting, but by itself would not mean we’ve found dark matter. When we’re in the realm of imagining new particles, there is a vast landscape of possibilities. Only some features in that landscape could qualify as dark matter; there are other possibilities that could exist but have nothing whatever to do with dark matter. So the properties of the particle have to be right, and there is a long list to satisfy.

\n\n\n\n

From a generic astronomical perspective, the fourth criterion is the most important. We have a pretty good idea of the mass density that dark matter needs to have in the solar neighborhood to explain Galactic kinematics. That’s what these experiments are trying to detect: the dark matter particles in our Galaxy’s dark matter halo that happen to be passing through just now. So for whatever we detect to qualify as the dark matter, there needs to be the right number of particles with the right mass to satisfy astronomical requirements.

\n\n\n\n

This fourth criterion is a pretty high bar. It does not suffice merely to find a new particle, it’s gotta be the right kind of particle and these particles have to exist with the right density. That can be measured, but it requires lots of detections: enough to work out the properties of the particles and how many are whizzing by. This is part of the disconnect I had in the last post with people complaining about statistical significance: they were focused on the significance of this one event; I was worried about having enough detections to estimate the mass density, or at least see if it is anywhere near the right ballpark. I’m more concerned with the astrophysical relevance of a new particle than with the new particle itself.

\n\n\n\n

This is a generic problem in the field of dark matter, being as it is at the interface of two different fields. Astronomers need dark matter; we don’t care so much what it is if it performs as required. Particle physicists heard we astronomers needed dark matter, so are more than happy to suggest possibilities, but are more interested in the particle itself than what it does for galaxies. I don’t say what it does for the universe because that’s a lower bar where any dynamically cold, non-baryonic mass will do. The cosmic density needs to be right, but there’s no way to measure the cosmic average, only the local density of the Galactic dark matter halo.

\n\n\n\n

The highest bar is the fifth criterion, which I think warrants its own post.

","doi":"https://doi.org/10.59350/3q11z-xt245","guid":"https://tritonstation.com/?p=13109","image":"https://tritonstation.com/wp-content/uploads/2026/09/nottheDMyourelookingofr.jpg","language":"en","license":"https://creativecommons.org/licenses/by/4.0/legalcode","published_at":1788998400,"rid":"0j7xh-d6340","summary":"I've been trying to think more seriously about the entity that set off the LZ experiment. I was dismissive of the possibility of it being dark matter, perhaps unfairly so. On further reflection, I feel only fairly dismissive.","tags":["Dark Matter","Particle Physics"],"title":"What can't it be?","updated_at":1789111809,"url":"https://tritonstation.com/2026/09/10/what-cant-it-be/","version":"v1"},{"authors":[{"contributor_roles":[],"family":"Crueger","given":"Jens"}],"blog":{"authors":[{"name":"Redaktion iRights.info"}],"community_id":"7d3b25fd-a4a8-4155-8e76-99d6be06706a","created":1694736000,"current_feed_url":null,"description":"Urheberrecht und kreatives Schaffen in der digitalen Welt","doi":"https://doi.org/10.59350/irights","favicon":"https://rogue-scholar.org/api/communities/7d3b25fd-a4a8-4155-8e76-99d6be06706a/logo","feed_format":"application/atom+xml","feed_url":"https://irights.info/feed/atom","filter":null,"generator":"Other","home_page_url":"https://irights.info/","issn":null,"language":"deu","license":"https://creativecommons.org/licenses/by/4.0/legalcode","prefix":"10.59350","relative_url":null,"secure":true,"slug":"irights","status":"active","subfield":"3308","title":"iRights.info","updated":1789026321,"use_api":false},"blog_name":"iRights.info","blog_slug":"irights","content_html":"

In the media and on social media, there has been a growing number of concerned reports about AI companies that are buying up used books in large quantities and in a rather ominous manner. It is speculated that the large quantities of books acquired in this way are scanned, used for AI training, and irretrievably destroyed in the process. It is often suggested that copyright law is the reason why the books are being destroyed. Can this assumption be substantiated?
\n

\n

The Destructive Scanning of Books

\n

The retro-digitization (usually referred to simply as \"digitization\") of books is typically carried out using scanning technology. Modern book scanners are capable of scanning books non-destructively. However, non-destructive scanning of books is a complex process, as irregularities caused by the book's binding must be compensated for during the scanning process.

\n

In contrast, in so-called destructive scanning, the book's binding is mechanically removed. This turns a book into a loose collection of pages that can be conveniently digitized using a sheet-fed scanner. Once the scanning process is complete, the book pages are then disposed of as waste paper.

\n

Why Antiquarian Bookstores Are Important for AI Training

\n

Digital data sources, such as web archives, have long been incorporated into the training of current AI models. The digitization of printed books is now the next stage in data acquisition. According to observers, tech companies are particularly focused on non-fiction books published between the 1970s and the 1990s.

\n

These books are likely to be of interest for three reasons: First, nonfiction books are valuable for AI training because of their content; they contain factual information that is still largely accurate and is integrated into linguistically sophisticated patterns of argumentation. Second, book titles published before the mid-1990s were generally released exclusively as print editions and have not been digitized since. Third, books from the period in question are still predominantly subject to copyright, which expires only 70 years after the author's death in both Germany and the U.S.

\n

Obtaining scans of these books from dubious third-party sources would be illegal. Therefore, from a copyright perspective, the purchased print editions of these books are particularly valuable to the companies.

\n

Technical Reasons for Destructive Scanning

\n

But why do AI companies accept the destruction of the books during the scanning process?

\n

First, technical aspects play a significant role in large-scale retro-digitization of books: As explained at the outset, destructive scanning is simpler, faster, and therefore more cost-effective. Although the AI industry appears economically strong, observers interpret the decision to use the most cost-effective digitization method as an indication of cost pressure in this \"highly competitive industry.\"

\n

Competitive considerations may also play a role, because while the books in question are not particularly old or unique, many of them are nevertheless rarely available on the antiquarian book market due to low print runs and scarcity. Whoever buys them first effectively removes them from the competition's reach, thereby gaining a small advantage for their AI model.

\n

Destructive Scanning Out of Concern for Copyright?

\n

A lawsuit between three plaintiff authors and the AI company Anthropic before the United States District Court for the Northern District of California (Bartz v. Anthropic) established a legal precedent regarding destructive book scanning in 2025.

\n

The central question here was whether destructive scanning, on the one hand, and the training of AI models using the content of acquired digitized books, on the other, fall under the so-called \"fair use principle.\"

\n
What is the fair use principle?
\nThe fair use principle is a legal doctrine found in some common law countries. It permits the use of copyrighted material for purposes of public education or intellectual production without requiring authorization for such use. Classic areas of application for fair use include commentary, criticism, parody, news reporting, research, and scholarship. Under German copyright law, instead of a general clause like fair use, there are narrow exceptions that permit certain uses (such as quotations, caricatures, parodies, educational and scholarly purposes, reporting on current events, etc.) regardless of the copyright holder's consent.
\n

The two central questions to be decided by the court must be considered separately:

\n

First, whether training AI models with the content of purchased digitized books is protected by the fair use doctrine.

\n

Second, whether destructive scanning constitutes a copyright-relevant copy of a work.

\n

According to Judge William Alsup, training AI models using the content of purchased digitized books was \"transformative in the truest sense of the word\" and therefore protected by the fair use doctrine. Destructive scanning should be classified as \"replacement scanning,\" in which a printed work is replaced by a digital work. This conversion of a purchased printed book into a digital book was classified by the court as a \"format change\" rather than a copy and is therefore also covered by fair use.

\n

A Landmark Ruling with Significant Implications

\n

The rule on format conversion\u2014also known as the \"format-shifting rationale\"\u2014thus promises, according to this landmark ruling, a certain degree of legal certainty for AI companies that destroy the books they have acquired for AI training through destructive scanning. The method that is more efficient from a technical standpoint is therefore also the more legally advisable one.

\n

However, it is a fallacy to assume that the court's ruling requires AI companies to destroy the digitized books. The lawsuit merely examined the specific digitization process as applied by Anthropic as part of \"Project Panama\"\u2014and classified it as fair use.

\n

E-books Instead of Print Books?

\n

If e-books were used for training instead of their printed counterparts, the time-consuming step of scanning\u2014and the associated issues of transportation, storage, and reuse\u2014would be eliminated.

\n

However, e-books can only become training data for AI models in two ways: the legal way\u2014that is, with the involvement of the rights holders of those e-books\u2014or by training with pirated copies. For AI companies, the legal route entails a significantly higher \"legal/practice/business slog\" (quote from Anthropic co-founder and CEO Dario Amodei).

\n

Training AI with pirated copies of e-books is not covered by fair use and thus constitutes a clear copyright infringement, Judge Alsup ruled.

\n

Fears of 'Fahrenheit 451' Scenarios

\n

Reports of AI companies purchasing large quantities of books from used bookstores have sparked, in some cases, fierce reactions in the media. The media discussion often references Ray Bradbury's novel *Fahrenheit 451*, a dystopia in which books are banned.

\n

A closer look at the relevant court ruling in this specific case reveals that there is no legal obligation to destroy retro-digitized books. Economic reasons for choosing the most cost-effective digitization method therefore appear to be the decisive factor when the AI industry employs destructive book scanning. Against the backdrop of the actions taken by major AI companies, calls for open-source AI models are currently growing louder, and with regard to the retro-digitization of books, there are also increasing calls for \"an open-source initiative or a similar nonprofit project.\"

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Would you like to support iRights.info?

\n

iRights.info provides information and explanations on the subject of \"Copyright and creativity in the digital world\". All texts are published free of charge and openly licensed.

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If you like, you can support us via the donation platform Betterplace and receive a donation receip. Betterplace accepts PayPal, direct debit, credit card, paydirekt or bank transfer.

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We would be particularly pleased to receive a regular contribution, for example as a monthly standing order. The non-profit organization iRights e.V. would like to thank you for your support!
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DOI for this text: \u00b7 Automatic DOI assignment for blogs via The Rogue Scholar

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The post Out of Concern for Copyright? AI Companies and Their Destructive Scanning of Books appeared first on iRights.info.

","doi":"https://doi.org/10.59350/ksfmn-23248","guid":"https://irights.info/?post_type=custom_artikel&p=32898","language":"en","license":"https://creativecommons.org/licenses/by/4.0/legalcode","published_at":1788998400,"rid":"bznwv-d6252","summary":"In the media and on social media, there has been a growing number of concerned reports about AI companies that are buying up used books in large quantities and in a rather ominous manner. It is speculated that the large quantities of books acquired in this way are scanned, used for AI training, and irretrievably [\u2026] The post Out of Concern for Copyright? AI Companies and Their Destructive Scanning of Books appeared first on iRights.info.","tags":["B\u00fccher","English","Generative KI","Urheberrecht","Urteile"],"title":"Out of Concern for Copyright? AI Companies and Their Destructive Scanning of Books","updated_at":1789111805,"url":"https://irights.info/artikel/out-of-concern-for-copyright-ai-companies-and-their-destructive-scanning-of-books/32898","version":"v1"},{"authors":[{"contributor_roles":[],"family":"Roddie","given":"Rosaria"}],"blog":{"authors":null,"community_id":"d6ac84f0-4643-4ec0-bcd0-e21306f31948","created":1707091200,"current_feed_url":null,"description":null,"doi":"https://doi.org/10.59350/europepmc","favicon":"https://rogue-scholar.org/api/communities/d6ac84f0-4643-4ec0-bcd0-e21306f31948/logo","feed_format":"application/atom+xml","feed_url":"https://blog.europepmc.org/feed/atom","filter":null,"generator":"WordPress","home_page_url":"https://blog.europepmc.org","issn":null,"language":"eng","license":"https://creativecommons.org/licenses/by/4.0/legalcode","prefix":"10.59350","relative_url":null,"secure":true,"slug":"europepmc","status":"active","subfield":"1710","title":"Europe PMC News Blog","updated":1789039109,"use_api":true},"blog_name":"Europe PMC News Blog","blog_slug":"europepmc","content_html":"

The Medical Research Council and Europe PMC are developing an open UK Health Research Funding Portfolio Database and Interactive Dashboard to make data on health research funding from participating UK public bodies and medical research charities easier to find, compare, and reuse.

\n\n\n\n

Across the UK, public bodies and medical research charities support a vast range of health research. The most recent UK Health Research Analysis  gives a sense of the scale: it covered more than 23,500 awards from 173 funding organisations and over \u00a35 billion in health research spending in 2022. For two decades, UK Health Research Analyses have shown the value of bringing this information together. However, they have provided only periodic historical snapshots rather than a dynamic view of the changing funding landscape. A timely view is needed to answer questions: Who is funding what? Where is research taking place? How is investment changing over time?

\n\n\n\n

The Medical Research Council (MRC), part of UK Research and Innovation (UKRI), is working with Europe PMC, hosted by EMBL-EBI, to develop the UK Health Research Funding Portfolio Database and Interactive Dashboard. The project is in response to Action 11.1 of the UK Government’s Life Sciences Sector Plan, which calls for closer coordination across health and life sciences funders.

\n\n\n\n

Planned for release in March 2027, the tool will use the established health and research activity classifications and a user-friendly dashboard to bring more of the breadth and diversity of this investment into a coherent, regularly updated view. The public-facing dashboard will make it easier to explore award data from participating UK funders. For example, a funder could compare the number and value of awards across years, examine investment by health category and research activity, and identify potential overlap or complementary activity. Researchers and institutions could see which funders and recipient organisations are active in related areas and where work is taking place. Industry and investors could use the same view to understand UK research strengths, see how investment is changing across locations and research areas, and identify potential partnership opportunities. 

\n\n\n\n

Europe PMC has long supported open science by linking grants to publications and other research outputs, and by making grant data openly available through its Grant Finder and application programming interface (API). Its integration of Research Organization Registry (ROR) identifiers into Grant Finder shows how persistent identifiers can connect variations in institutional names and make grant searches more consistent. The project will build on Europe PMC’s well-established grant-data infrastructure. Existing Europe PMC grant data provides a strong foundation, while contributions from UK Governmental bodies and medical research charities\u2014including organisations outside the Europe PMC funder group\u2014will be essential to creating a representative national picture.

\n\n\n\n

A UK focus with wider benefits

\n\n\n\n

Although the data resulting from this project is UK-focussed for now, responding to a specific UK governmental policy commitment, the expanded data model remains applicable for Europe PMC's international funder group. GRIST, the longstanding infrastructure that supports Europe PMC funders in linking grants to research outputs, will be rebuilt as a modern, scalable, open-source infrastructure. Submission and correction workflows will be improved, alongside stronger validation and deduplication. The open GRIST API will expose the expanded data and, for Europe PMC funders, provide links from grants to publications and research data, helping users understand the outputs and wider impact of investment. Together, these changes are intended to improve data quality, reduce manual intervention over time and make grant data easier to maintain and reuse. Future growth of the tool could incorporate further datasets and categorisation.

\n\n\n\n

Why funder participation matters

\n\n\n\n

The value of the dashboard will depend on the quality and coverage of the data contributed to it. Participating funders will provide and update award records through agreed submission routes, while validation and correction processes will help ensure that investments are represented accurately and consistently. 

\n\n\n\n

We welcome interest from UK public bodies and medical research charities that fund health research. To learn more about participating, contact Rosa at roddie@ebi.ac.uk.

\n\n\n\n

Related links

\n\n\n\n

UK Health Research Analysis 2022\u00a0 |\u00a0 Life Sciences Sector Plan\u00a0 |\u00a0 Medical Research Council\u00a0 |\u00a0 Europe PMC\u00a0 |\u00a0 Europe PMC Grant Finder

","doi":"https://doi.org/10.59350/wxpmx-3hq18","guid":"https://blog.europepmc.org/?p=1747","language":"en","license":"https://creativecommons.org/licenses/by/4.0/legalcode","published_at":1788998400,"rid":"r0mhr-85224","summary":"The Medical Research Council and Europe PMC are developing an open UK Health Research Funding Portfolio Database and Interactive Dashboard to make data on health research funding from participating UK public bodies and medical research charities easier to find, compare, and reuse.","tags":["Funders","Grant Data","Grant Reporting","GRIST API"],"title":"Building a clear picture of UK health research funding","updated_at":1789111805,"url":"https://blog.europepmc.org/2026/09/building-a-clear-picture-of-uk-health-research-funding.html","version":"v1"},{"authors":[{"affiliation":[{"name":"University of Wroc\u0142aw, Chemistry"}],"contributor_roles":[],"family":"Janeta","given":"Mateusz","url":"https://orcid.org/0000-0003-2197-7913"}],"blog":{"authors":null,"community_id":"c21eed24-c860-43d0-997c-0bc782922544","created":1788652800,"current_feed_url":null,"description":null,"doi":"https://doi.org/10.59350/silsesquioxane","favicon":"https://rogue-scholar.org/api/communities/c21eed24-c860-43d0-997c-0bc782922544/logo","feed_format":"application/atom+xml","feed_url":"https://silsesquioxane.blogspot.com/feeds/posts/default","filter":null,"generator":"Blogger","home_page_url":"https://silsesquioxane.blogspot.com/","issn":null,"language":"eng","license":"https://creativecommons.org/licenses/by/4.0/legalcode","prefix":"10.59350","relative_url":null,"secure":true,"slug":"silsesquioxane","status":"active","subfield":"1604","title":"Polyhedral Oligomeric Silsesquioxane (POSS) Chemistry","updated":1789050682,"use_api":true},"blog_name":"Polyhedral Oligomeric Silsesquioxane (POSS) Chemistry","blog_slug":"silsesquioxane","content_html":"

\u4e2d\u6587\u7248\u672c / Chinese version: POSS \u4e8c\u6c1f\u787c\u5149\u50ac\u5316\u5242:\u786b\u919a\u9009\u62e9\u6027\u6c27\u5316\u5236\u4e9a\u781c

\n

\"silsesquioxaneThe publication titled \"Polyhedral oligomeric silsesquioxane difluoroboron complexes as cooperative octo-site catalysts for the photooxidation of sulfides to sulfoxides\" by Mateusz Janeta and S\u0142awomir Szafert, published in Inorganic Chemistry Frontiers on April 17, 2025, presents a study on the development of novel metal-free photocatalysts. These catalysts are based on polyhedral oligomeric silsesquioxanes (POSS) functionalized with difluoroboron complexes.

\"Synthetic
Scheme 1. Synthesis of POSS-sal-BF2, POSS-tert-BF2, and POSS-npht-BF2. Isolated yields in parentheses.

Key Highlights

This research underscores the potential of POSS-based difluoroboron complexes as efficient, sustainable, and reusable photocatalysts for the selective oxidation of sulfides to sulfoxides, with implications for pharmaceutical synthesis and environmental applications.

Singlet Oxygen Quantum Yields

The singlet oxygen quantum yield (SOQY, \u03a6(1O2)) was determined by monitoring the photooxidation of DPA in methanol in the presence of the POSS derivatives. Changes in the DPA absorbance at 391 nm were measured over time using low concentrations of photosensitizer and DPA in order to minimize potential quenching of 1O2 by the photocatalyst. The SOQY values were calculated by plotting the change in DPA absorbance against irradiation time.

The calculated \u03a6(1O2) values for POSS-tert-BF2, POSS-sal-BF2, POSS-npht-BF2, prop-tert-BF2, prop-sal-BF2, and prop-npht-BF2 were 48%, 35%, 46%, 27%, 26%, and 18%, respectively, which highlights the high efficiency of POSS-tert-BF2 in generating singlet oxygen. A higher singlet oxygen quantum yield, and therefore a higher degree of DPA oxidation, was obtained for the octametallic POSS-tert-BF2, POSS-sal-BF2, and POSS-npht-BF2 than for the monometallic analogues prop-tert-BF2, prop-sal-BF2, and prop-npht-BF2 under the same reaction conditions. This can be attributed to the intramolecular cooperative effect in compounds bearing the POSS moiety, which was investigated further.

Photocatalytic Oxidation of Sulfides to Sulfoxides

Recent studies have demonstrated the powerful photocatalytic capabilities of POSS-tert-BF2, a boron difluoride-functionalized polyhedral oligomeric silsesquioxane. This system shows a significant singlet oxygen quantum yield and generates multiple reactive oxygen species, which makes it highly effective in oxidative transformations.

\"Photooxidation

Key findings from the study

The conversion of thioanisole was only 30% in pure DCM, whereas under the same reaction conditions in MeOH the conversion increased to 99%. Protic solvents such as MeOH and H2O are known to stabilize the intermediate involved in the formation of 1O2 and thereby to accelerate photooxidation. These differences in conversion also suggest that 1O2 can be identified as one of the reactive oxygen species involved in the photooxidation of thioanisole.

Comparing the activity of POSS compounds bearing various substituents on the phenyl ring, we observed that introducing steric hindrance, as in the tert-butyl groups at the 3- and 5-positions of the phenyl ring in POSS-tert-BF2, significantly increased the reaction efficiency, giving 99% conversion in 40 minutes compared with 70% for POSS-sal-BF2, which lacks bulky substituents. Introducing steric hindrance at the 5,6-positions of the phenyl ring in POSS-npht-BF2, by replacing the phenyl ring with a naphthalene ring, also improved the efficiency relative to POSS-sal-BF2, although it remained lower than that of POSS-tert-BF2. This underscores the critical role of steric hindrance at the 3-position of the phenyl ring in promoting the conversion of thioanisole. POSS-tert-BF2 therefore exhibits high efficiency in the photocatalytic oxidation of thioanisole and was studied in greater detail.

The reaction progress was monitored in real time by NMR spectroscopy, which revealed that the conversion of thioanisole to methyl phenyl sulfoxide with POSS-tert-BF2 as the photosensitizer increased steadily over time, reaching complete conversion within 40 minutes in accordance with zero-order kinetics. By comparison, the use of prop-tert-BF2 resulted in only 65% substrate conversion after 40 minutes, with full conversion achieved after 60 minutes. These findings clearly demonstrate the superior reaction efficiency and faster catalytic performance of POSS-tert-BF2 relative to prop-tert-BF2.

The higher conversion of thioanisole obtained with the octametallic POSS-tert-BF2 (99%) than with the monometallic analogue prop-tert-BF2 (65%) under the same reaction conditions supports the occurrence of intramolecular cooperative catalysis in POSS-tert-BF2. This observation is consistent with the enhancement recorded in the singlet oxygen quantum yields. A similar intramolecular cooperative effect was previously reported for Zn4@POSS-1, which contains the POSS-1 ligand, in the formation of cyclic carbonates from epoxides.37 A comparable enhancement in efficiency was observed for POSS-sal-BF2 and POSS-npht-BF2. Comparing the activity of POSS-npht-BF2 with that of prop-npht-BF2, a higher yield of 90% versus 60% was obtained for POSS-npht-BF2. The activity of POSS-sal-BF2 is likewise higher than that of prop-sal-BF2, at 70% versus 59%.

\"Proposed
Scheme 2. Proposed reaction mechanisms of sulfide-selective oxidation by POSS-tert-BF2 in the presence of O2.

Substrate Scope

To assess the versatility of POSS-tert-BF2 as a photocatalyst in the photooxidation of thioanisole derivatives in methanol, a series of substrates bearing various substituents was evaluated. Thioanisole derivatives containing the electron-donating group \u2013CH3 and the electron-withdrawing groups \u2013CN, \u2013CHO, and \u2013C(O)CH3 achieved high yields of 99%, 82%, 78%, and 96%, respectively. Bromine-substituted derivatives at the ortho and meta positions also gave high yields of 99%.

\"Substrate

These results highlight the potential of POSS-based systems in green and efficient photocatalytic oxidation chemistry.

Full CitationMateusz Janeta and S\u0142awomir Szafert. \"Polyhedral oligomeric silsesquioxane difluoroboron complexes as cooperative octo-site catalysts for the photooxidation of sulfides to sulfoxides.\" Inorganic Chemistry Frontiers, 2025, 12, 4666-4676.
DOI: 10.1039/D5QI00323G
Full text: Inorganic Chemistry Frontiers \u2192 RSC Publishing
\"Research
","doi":"https://doi.org/10.59350/pznaw-y5e39","guid":"tag:blogger.com,1999:blog-2875892712213933214.post-4039579808081725822","image":"https://blogger.googleusercontent.com/img/b/R29vZ2xl/AVvXsEieZxQDVRgNeI8fmnmqP8Q-yYBJlE79nqTichFmo5SytMhZfFD9URo5d6StOfaKM95COqeqIfh2B72C6LWys5dyJBBhR_9TiY3UJG08-bqRwv6I6yfBgCvyAfYfQ3BvBcaZ5gedOnqAAkaqMwyhpv_luxChyTOmfKo_RZwCcEmXc_iEntpFdRVVGSMD-6g/s72-w99-h91-c/Research%20Highlights%20-%20Copy.png","language":"en","license":"https://creativecommons.org/licenses/by/4.0/legalcode","published_at":1788998400,"rid":"8jtxv-rdg17","summary":"\u4e2d\u6587\u7248\u672c / Chinese version: POSS \u4e8c\u6c1f\u787c\u5149\u50ac\u5316\u5242:\u786b\u919a\u9009\u62e9\u6027\u6c27\u5316\u5236\u4e9a\u781c The publication titled \"Polyhedral oligomeric silsesquioxane difluoroboron complexes as cooperative octo-site catalysts for the photooxidation of sulfides to sulfoxides\" by Mateusz Janeta and S\u0142awomir Szafert, published in Inorganic Chemistry Frontiers on April 17, 2025, presents a study on the development of novel metal-free photocatalysts.","tags":["Catalysis","Imine-POSS","Photochemistry","POSS","POSS Functionalization"],"title":"POSS Difluoroboron Photocatalysts for Sulfide Oxidation","updated_at":1789025423,"url":"https://silsesquioxane.blogspot.com/2026/09/poss-difluoroboron-photocatalysts-for.html","version":"v1"},{"authors":[{"affiliation":[{"name":"Bielefeld University, Medical Faculty"}],"contributor_roles":[],"family":"Friederichs","given":"Hendrik","url":"https://orcid.org/0000-0001-9671-5235"}],"blog":{"authors":null,"community_id":"304adf51-cbb7-4ff1-a505-1dc06082fbad","created":1776988800,"current_feed_url":null,"description":"Aktuelle Einblicke aus der medizinischen Bildungsforschung \u2014 evidenzbasiert, verst\u00e4ndlich, mit gelegentlichem Augenzwinkern.","doi":"https://doi.org/10.59350/medical_education","favicon":"https://rogue-scholar.org/api/communities/304adf51-cbb7-4ff1-a505-1dc06082fbad/logo","feed_format":"application/rss+xml","feed_url":"https://medical-education.pages.ub.uni-bielefeld.de/research/mes-blog/blog.xml","filter":null,"generator":"Quarto","home_page_url":"https://medical-education.pages.ub.uni-bielefeld.de/research/mes-blog/blog.html","issn":null,"language":"eng","license":"https://creativecommons.org/licenses/by/4.0/legalcode","prefix":"10.59350","relative_url":null,"secure":true,"slug":"medical_education","status":"active","subfield":"2739","title":"Entscheiden(d) lernen","updated":1788991200,"use_api":null},"blog_name":"Entscheiden(d) lernen","blog_slug":"medical_education","content_html":"

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Im Oktober beginnen viele junge Menschen ihr Medizinstudium. Viele von ihnen werden in den ersten Wochen denselben Gedanken haben, n\u00e4mlich dass alle anderen im H\u00f6rsaal besser vorbereitet, kl\u00fcger und sicherer wirken als sie selbst. Dieser Gedanke hat einen Namen, er ist gut untersucht, und er ist erstaunlich verbreitet.

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Der Gedanke in der ersten Woche

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Die allererste Vorlesung. Um Euch herum sitzen Leute, die sich offenbar m\u00fchelos Fachbegriffe merken, die im Seminar als Erste die Hand heben und die schon wissen, wo die Bibliothek ist. Ihr selbst habt das Gef\u00fchl, durch einen Zufall hier gelandet zu sein. Die Zulassung war Gl\u00fcck, der gute Abiturschnitt eine Verkettung g\u00fcnstiger Umst\u00e4nde, und irgendwann wird jemand merken, dass Ihr eigentlich gar nicht hierhergeh\u00f6rt.

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Wenn Euch das bekannt vorkommt, seid Ihr in gro\u00dfer Gesellschaft. Zwei Metaanalysen aus diesem Jahr kommen unabh\u00e4ngig voneinander zu dem Ergebnis, dass etwa die H\u00e4lfte aller Medizinstudierenden weltweit ausgepr\u00e4gte Impostor-Gef\u00fchle berichtet [1, 2]. Zum Studienstart liegt der Anteil noch deutlich h\u00f6her. In einer L\u00e4ngsschnittstudie mit 257 Erstsemestern hatten fast neun von zehn schon in den ersten Wochen hohe Werte, und bis zum Jahresende stiegen sie weiter [3].

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Was das Impostor-Ph\u00e4nomen ist

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Beschrieben haben es die Psychologinnen Pauline Clance und Suzanne Imes 1978 bei mehr als 150 beruflich sehr erfolgreichen Frauen. Ihre Klientinnen waren \u00fcberzeugt, ihre Erfolge nicht verdient zu haben, und lebten in der Erwartung, irgendwann als Betr\u00fcgerinnen entlarvt zu werden [4]. Das T\u00fcckische daran ist ein Kreislauf. Wer vor einer Pr\u00fcfung \u00fcberm\u00e4\u00dfig viel lernt und besteht, schreibt das dem Flei\u00df zu, nicht der eigenen F\u00e4higkeit. Wer aufgeschoben hat und trotzdem durchkommt, schreibt es dem Gl\u00fcck zu. In beiden F\u00e4llen bleibt die eigene Kompetenz unsichtbar, und die n\u00e4chste Pr\u00fcfung beginnt mit denselben Zweifeln.

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Zwei Dinge sind dabei wichtig. Das Impostor-Ph\u00e4nomen ist keine Krankheit und keine Diagnose, es steht in keinem Klassifikationssystem. Und der verbreitete Begriff \"Impostor-Syndrom\" f\u00fchrt in die Irre, weil er nahelegt, das Problem s\u00e4\u00dfe in der Person. Eine Forschungsgruppe hat 2020 daf\u00fcr pl\u00e4diert, das Ph\u00e4nomen konsequent im Kontext zu betrachten, also in den Umgebungen, die solche Gef\u00fchle hervorrufen [5]. Genau darum geht es im n\u00e4chsten Abschnitt.

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Warum ausgerechnet das Medizinstudium

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Die Antwort beginnt mit der Auswahl. Wer einen Medizinstudienplatz bekommt, geh\u00f6rte an der Schule zu den Besten. Im H\u00f6rsaal sitzen dann 300 Menschen, auf die das gleiche zutrifft, und die vertraute Referenzgruppe ist \u00fcber Nacht verschwunden. Wer sich bisher am oberen Rand verortet hat, findet sich pl\u00f6tzlich in der Mitte wieder, ohne dass sich an den eigenen F\u00e4higkeiten etwas ge\u00e4ndert h\u00e4tte.

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Dazu kommt eine Kultur, die Perfektion als Normalzustand behandelt. Ein \u00dcberblick \u00fcber die Literatur beschreibt, wie das Medizinstudium hohe Anspr\u00fcche und Selbstkritik nicht nur anzieht, sondern aktiv trainiert [6]. Eine britische Studie fand, dass die Impostor-Werte umso h\u00f6her lagen, je weiter unten jemand im Pr\u00fcfungsranking stand [7]. Das klingt zun\u00e4chst naheliegend, hat aber eine Pointe. In einer Gruppe, in der alle zu den Besten ihres Jahrgangs geh\u00f6rten, muss ein Ranking trotzdem die H\u00e4lfte in die untere H\u00e4lfte sortieren. Es verteilt also Zweifel an Menschen, deren Leistung sich gar nicht verschlechtert hat.

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Ein dritter Faktor ist die Frage, ob man sich zugeh\u00f6rig f\u00fchlt. Kanadische Studierende, die im Studium erlebten, dass sie etwas k\u00f6nnen und dass sie aus eigenem Antrieb lernen, berichteten deutlich weniger Impostor-Gef\u00fchle. Wer sich dagegen vor allem von au\u00dfen getrieben f\u00fchlte, von Noten, Erwartungen und Vergleich, berichtete mehr davon [8]. Und wer an seiner Fakult\u00e4t zu einer Minderheit geh\u00f6rt, ist besonders betroffen. In den USA berichteten Studierende aus unterrepr\u00e4sentierten Gruppen an \u00fcberwiegend wei\u00dfen Fakult\u00e4ten fast dreimal so h\u00e4ufig starke Impostor-Gef\u00fchle wie an Hochschulen mit \u00fcberwiegend schwarzer Studierendenschaft [9].

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Das Impostor-Gef\u00fchl ist also weniger eine Eigenschaft, die man mitbringt, als eine Reaktion auf eine Situation. Das erkl\u00e4rt, warum es in \u00dcbergangsphasen am st\u00e4rksten ist, nach dem Studienstart, beim Eintritt in die Klinik, zu Beginn der Weiterbildung. So z. B. hatten britische Chirurg*innen in Weiterbildung deutlich h\u00f6here Werte als ihre fertig ausgebildeten Kolleg*innen [10]. Es wird besser, aber nicht von allein und nicht schnell.

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Warum es nicht egal ist

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Man k\u00f6nnte einwenden, ein bisschen Selbstzweifel schadet nicht. Ein bisschen stimmt das auch. Problematisch wird es, wenn die Zweifel anhalten. Bei \u00c4rzt*innen in Weiterbildung war ein ausgepr\u00e4gtes Impostor-Erleben ein eigenst\u00e4ndiger Risikofaktor f\u00fcr Angstsymptome und Burnout [11], und bei einer Studie an mehr als 3.000 US-\u00c4rzt*innen verdoppelte es die Wahrscheinlichkeit f\u00fcr Burnout [12]. Bei Erstsemestern hing anhaltendes Impostor-Erleben mit geringerem Selbstmitgef\u00fchl und mehr psychischer Belastung zusammen [3]. Wer merkt, dass die Zweifel nicht mehr nur vor Pr\u00fcfungen kommen, sondern den Alltag bestimmen, sollte das ernst nehmen und die Beratungsangebote der Universit\u00e4t nutzen. Die sind genau daf\u00fcr da.

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Was hilft

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Noch 2020 stellte das gr\u00f6\u00dfte systematische Review zum Thema fest, dass es keine einzige evaluierte Ma\u00dfnahme gegen das Impostor-Ph\u00e4nomen gab [13]. Seitdem hat sich einiges getan.

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Am besten belegt ist Gruppencoaching. In zwei randomisierten Studien mit zusammen mehr als 1.100 \u00c4rztinnen in Weiterbildung senkte ein sechsmonatiges Online-Programm Impostor-Werte und emotionale Ersch\u00f6pfung und st\u00e4rkte das Selbstmitgef\u00fchl [14, 15]. Ein Umbrella-Review von 2026, das 16 \u00dcbersichtsarbeiten zusammenfasst, sieht Potenzial in Coaching, Online-Modulen und achtsamkeitsbasierten Ans\u00e4tzen, mahnt aber, dass hochwertige Interventionsstudien noch selten sind [16].

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F\u00fcr den Studienstart ist ein anderer Befund vielleicht wichtiger. Schon ein einzelner Workshop, in dem Erstsemester das Ph\u00e4nomen kennenlernen und merken, dass es fast allen so geht, ver\u00e4ndert etwas. Nach einem solchen Workshop konnten neun von zehn Erstsemestern das Muster bei sich selbst erkennen [17], und in einer Orientierungswoche sank der Anteil mit starken Impostor-Gef\u00fchlen um zehn Prozentpunkte [18]. Der Wirkmechanismus hei\u00dft Normalisierung. Das Gef\u00fchl, allein damit zu sein, ist ein gro\u00dfer Teil des Problems, und es l\u00f6st sich in dem Moment auf, in dem die Nachbarin im H\u00f6rsaal dasselbe erz\u00e4hlt. Strukturierte Peer-Treffen f\u00fcr Studienanf\u00e4nger*innen zielen genau darauf [19].

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Was Ihr selbst tun k\u00f6nnt, l\u00e4sst sich aus dieser Evidenz ableiten. Redet dar\u00fcber, mit Kommiliton*innen und mit Lehrenden, denn die Wahrscheinlichkeit, dass Euer Gegen\u00fcber es kennt, liegt bei etwa f\u00fcnfzig Prozent. Schreibt Euch auf, was Ihr gut k\u00f6nnt, nicht nur, was Ihr noch nicht k\u00f6nnt, denn der Impostor-Kreislauf lebt davon, Erfolge zu vergessen. Und wechselt den Vergleichsma\u00dfstab. Die Frage ist nicht, ob Ihr besser seid als die Person neben Euch, sondern ob Ihr mehr k\u00f6nnt als vor vier Wochen.

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\nTippF\u00fcr Statistik-Interessierte \u2014 die Zahlen hinter dem Impostor-Ph\u00e4nomen\n
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Die meisten Studien nutzen die Clance Impostor Phenomenon Scale (CIPS, 20 Items, Wertebereich 20 bis 100). Ab 62 Punkten gelten Impostor-Gef\u00fchle als \"h\u00e4ufig\", ab 81 als \"intensiv\". Diese Grenzen sind Konvention, nicht Diagnosekriterium, und sie erkl\u00e4ren einen Teil der Streuung zwischen den Studien.

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Zwei Metaanalysen, ein Bild. Omar et al.\u00a0poolten 34 Studien mit 9.550 Medizinstudierenden und fanden eine Pr\u00e4valenz von 49 % (95 %-KI 43 bis 54 %, I\u00b2 = 95,6 %). Frauen lagen bei 51 %, M\u00e4nner bei 40 % (p = 0,021). Mit der CIPS ergaben sich 53 %, mit der Young Impostor Scale 38 % [1]. Vera-Ponce et al.\u00a0poolten 26 CIPS-Studien mit 9.110 Studierenden und kamen auf 54,2 % (95 %-KI 47,0 bis 61,3 %, I\u00b2 = 98 %), ohne Unterschied zwischen vorklinischem (48,9 %) und klinischem Abschnitt (46,8 %, !) und ohne zeitlichen Trend zwischen 2018 und 2024 [2]. Bei I\u00b2-Werten \u00fcber 95 % beschreibt der gepoolte Wert eine Gr\u00f6\u00dfenordnung, keine gemeinsame Realit\u00e4t.

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Der Studienstart in Zahlen. Rosenthal et al.\u00a0befragten 257 Erstsemester zu Beginn und am Ende des ersten Jahres. 87 % hatten anfangs hohe oder sehr hohe Werte, die bis zum Jahresende signifikant anstiegen (p < 0,001). Hohe Werte gingen mit deutlich geringerem Selbstmitgef\u00fchl einher (d = 1,62) [3]. Houseknecht et al.\u00a0beobachteten 110 Studierende \u00fcber drei Jahre und fanden steigende Impostor-Werte (p = 0,011) bei sinkender professioneller Identifikation [20]. Kim et al.\u00a0verfolgten eine Kohorte von der Orientierungswoche bis zum Ende des 16-monatigen vorklinischen Abschnitts. Der mittlere CIPS-Wert blieb praktisch unver\u00e4ndert (68,3 gegen\u00fcber 68,1), die Ausl\u00f6ser verschoben sich aber vom Zulassungsgl\u00fcck zum Vergleich mit anderen [21].

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Europ\u00e4ische Stichproben. Unter 457 schwedischen Medizinstudierenden lagen 58,4 % \u00fcber dem CIPS-Grenzwert, Frauen mit 67,4 gegen\u00fcber 59,3 Punkten (d = 0,47). Resilienz korrelierte moderat negativ mit Impostor-Werten (r = \u22120,41) [22]. In Ume\u00e5 lagen 64 % von 968 Studierenden verschiedener F\u00e4cher \u00fcber dem Grenzwert, und weder Semester noch Alter machten einen Unterschied [23]. F\u00fcr Deutschland gibt es bislang keine vergleichbare Erhebung.

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Umgebung und Ranking. Franchi und Russell-Sewell fanden bei 191 britischen Studierenden einen mittleren CIPS-Wert von 65,8, bei 65,4 % \u00fcber dem Grenzwert; pro Dezil weiter unten im Pr\u00fcfungsranking stieg der Wert um 1,12 Punkte (p < 0,05) [7]. Bei Neufeld et al.\u00a0erkl\u00e4rte die Befriedigung der psychologischen Grundbed\u00fcrfnisse 21,8 % der Varianz, das Kompetenzerleben allein hatte ein \u03b2 von \u22120,49 [8]. Rice et al.\u00a0berichten f\u00fcr Studierende aus unterrepr\u00e4sentierten Gruppen an \u00fcberwiegend wei\u00dfen Fakult\u00e4ten eine Odds Ratio von 2,75 (95 %-KI 1,65 bis 4,58) gegen\u00fcber historisch schwarzen Hochschulen [9]. In der britischen Unfallchirurgie lagen Trainees bei 70,6 Punkten, Consultants bei 59,8 [10].

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Folgen. Bei 269 \u00c4rzt*innen in Weiterbildung war das Impostor-Erleben ein unabh\u00e4ngiger Risikofaktor f\u00fcr Angst (RR = 3,64; 95 %-KI 1,96 bis 6,76) und Burnout (RR = 1,82; 95 %-KI 1,07 bis 3,08) [11]. Bei 3.116 US-\u00c4rzt*innen war intensives Impostor-Erleben mit h\u00f6heren Odds f\u00fcr Burnout (OR = 2,13; 95 %-KI 1,43 bis 3,19) und f\u00fcr Suizidgedanken (OR = 2,62; 95 %-KI 1,46 bis 4,65) verbunden [12]. Bei 226 Medizinstudierenden vermittelte das Impostor-Ph\u00e4nomen den Zusammenhang zwischen maladaptivem Perfektionismus und Suizidgedanken (indirekter Effekt B = 0,07; 95 %-KI 0,03 bis 0,13); das ist eine Mediation in Querschnittsdaten, keine Kausalkette [24].

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Interventionen. Fainstad et al.\u00a0randomisierten 101 Assistenz\u00e4rztinnen; das Impostor-Ma\u00df sank in der Coaching-Gruppe um 1,16 Punkte und stieg in der Kontrollgruppe um 0,11 (p = 0,003) [14]. Die multizentrische Replikation mit 1.017 Teilnehmerinnen fand eine Differenz von \u22121,28 Punkten (95 %-KI \u22121,63 bis \u22120,93) [15]. Nach zw\u00f6lf Monaten war der Impostor-Effekt nicht mehr signifikant (p = 0,081), das Selbstmitgef\u00fchl blieb verbessert [25]. Ein systematisches Review von sechs Online-Interventionen fand nur zwei RCTs [26]. Die Orientierungswochen-Workshops sind unkontrollierte Vorher-Nachher-Vergleiche, mit 53 % gegen\u00fcber 43 % mit h\u00e4ufigem oder intensivem Impostor-Erleben bei 222 Studierenden [18], 91,6 % Wiedererkennung bei 49 Erstsemestern [17], 96 % bei 21 Assistenz\u00e4rzt*innen [27].

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Was wir (noch) nicht wissen

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Fazit

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\nHinweisTransparenzkasten\n
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Transparenzhinweis:

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  • Interessenkonflikte: Keine angegeben.
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  • Finanzierung: Keine Angabe.
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  • KI-Nutzung: Claude (Anthropic) wurde zur strukturellen Konzeption und zur sprachlichen Bearbeitung auf Basis eines vom Autor verfassten und immer wieder \u00fcberarbeiteten Gedankengangs eingesetzt.
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  • Eigene Beteiligung: Der Autor ist in der medizinischen Ausbildungsforschung t\u00e4tig und hat auch mal Medizin studiert. Obwohl er heute Arzt und Professor ist, ist er im Studium durch Pr\u00fcfungen durchgefallen und kennt das Impostor-Gef\u00fchl sehr gut (auch wenn er das damals nicht so sch\u00f6n benennen konnte).
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Referenzen

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\n1. Omar YM, Khattab YA, Abdelmageed A, Messak M, Mandour Y, Shabeeb AE, u.\u00a0a. The impostor phenomenon construct in medical education: a meta-analysis of its prevalence and a critical appraisal of its measurement. Advances in Health Sciences Education. 2026. https://doi.org/10.1007/s10459-026-10513-3.\n
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\n2. Vera-Ponce VJ, Huaman-Vega CH, Zuzunaga-Montoya FE, Guerrero Uceda CI, Le\u00f3n-Figueroa DA, Rivera-Lozada O, u.\u00a0a. Global prevalence of impostor phenomenon in medical students: A systematic review and meta-analysis. PLOS One. 2026;21:e0351713.\n
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\n3. Rosenthal S, Schlussel Y, Yaden MB, DeSantis J, Trayes K, Pohl C, u.\u00a0a. Persistent Impostor Phenomenon Is Associated With Distress in Medical Students. Family Medicine. 2021;53:118\u201322.\n
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\n4. Clance PR, Imes SA. The imposter phenomenon in high achieving women: Dynamics and therapeutic intervention. Psychotherapy: Theory, Research &amp; Practice. 1978;15:241\u20137.\n
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\n5. Feenstra S, Begeny CT, Ryan MK, Rink FA, Stoker JI, Jordan J. Contextualizing the Impostor \"Syndrome\". Frontiers in Psychology. 2020;11.\n
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\n6. Thomas M, Bigatti S. Perfectionism, impostor phenomenon, and mental health in medicine: a literature review. International Journal of Medical Education. 2020;11:201\u201313.\n
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\n7. Franchi T, Russell-Sewell N. Medical Students and the Impostor Phenomenon: A Coexistence Precipitated and Perpetuated by the Educational Environment? Medical Science Educator. 2022;33:27\u201338.\n
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\n8. Neufeld A, Babenko O, Lai H, Svrcek C, Malin G. Why Do We Feel Like Intellectual Frauds? A Self-Determination Theory Perspective on the Impostor Phenomenon in Medical Students. Teaching and Learning in Medicine. 2022;35:180\u201392.\n
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\n9. Rice J, Rosario-Williams B, Williams F, West-Livingston L, Savage D, Wilensky JA, u.\u00a0a. Impostor syndrome among minority medical students who are underrepresented in medicine. Journal of the National Medical Association. 2023;115:191\u20138.\n
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\n10. Kamran Siddiqui Z, Tomlinson J, Scantlebury A, Jayasuriya R, Church H, Grove A. Hidden barriers to leadership: a cross-sectional survey of prevalence and predictors of Imposter Phenomenon in Trauma and Orthopaedic surgery in the UK. BMJ Open. 2025;15:e100557.\n
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\n11. Liu RQ, Davidson J, Van Hooren TA, Van Koughnett JAM, Jones S, Ott MC. Impostorism and anxiety contribute to burnout among resident physicians. Medical Teacher. 2022;44:758\u201364.\n
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\n12. Shanafelt TD, Dyrbye LN, Sinsky C, Trockel M, Makowski MS, Tutty M, u.\u00a0a. Imposter Phenomenon in US Physicians Relative to the US Working Population. Mayo Clinic Proceedings. 2022;97:1981\u201393.\n
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\n13. Bravata DM, Watts SA, Keefer AL, Madhusudhan DK, Taylor KT, Clark DM, u.\u00a0a. Prevalence, Predictors, and Treatment of Impostor Syndrome: a Systematic Review. Journal of General Internal Medicine. 2019;35:1252\u201375.\n
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\n14. Fainstad T, Mann A, Suresh K, Shah P, Dieujuste N, Thurmon K, u.\u00a0a. Effect of a Novel Online Group-Coaching Program to Reduce Burnout in Female Resident Physicians: A Randomized Clinical Trial. JAMA Network Open. 2022;5:e2210752.\n
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\n15. Mann A, Shah AN, Thibodeau PS, Dyrbye L, Syed A, Woodward MA, u.\u00a0a. Online Well-Being Group Coaching Program for Women Physician Trainees: A Randomized Clinical Trial. JAMA Network Open. 2023;6:e2335541.\n
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\n16. Gisselbaek M, Seyour M, Saxena S, Berger\u2010Estilita J, LaDonna KA, Elia N, u.\u00a0a. Rethinking the impostor phenomenon: An umbrella review of concept, context and interventions. Medical Education. 2025;60:607\u201324.\n
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\n17. Wrench A, Padilla M, O'Malley C, Levy A. Impostor phenomenon: Prevalence among 1st year medical students and strategies for mitigation. Heliyon. 2024;10:e29478.\n
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\n18. Kim E, Dupont J, Durning SJ, Landoll R, Soh M. Mitigating Impostor Phenomenon of Onboarding Military Medical Students: A Workshop Utilizing Situated Learning Theory. Military Medicine. 2025;190:e2153\u20139.\n
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\n20. Houseknecht VE, Roman B, Stolfi A, Borges NJ. A Longitudinal Assessment of Professional Identity, Wellness, Imposter Phenomenon, and Calling to Medicine Among Medical Students. Medical Science Educator. 2019;29:493\u20137.\n
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\n21. Kim E, Dupont J, Durning SJ, Bulaklak J, Crosier A, Soh M. Exploring Impostor Phenomenon During Pre-Clerkship Period in Military Medical School. Military Medicine. 2025;191:e413\u201320.\n
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\n23. Jansson A, Boman J, Sch\u00e9le I, Holmstr\u00f6m S, Rozental A, Semb O, u.\u00a0a. Impostor phenomenon and its association with perceived stress and anxiety among students in medical and social sciences at a Swedish university. Frontiers in Medicine. 2025;12.\n
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\n24. Brennan-Wydra E, Chung HW, Angoff N, ChenFeng J, Phillips A, Schreiber J, u.\u00a0a. Maladaptive Perfectionism, Impostor Phenomenon, and Suicidal Ideation Among Medical Students. Academic Psychiatry. 2021;45:708\u201315.\n
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\n25. Fainstad T, Syed A, Thibodeau PS, Vinaithirthan V, Jones CD, Mann A. Long-Term Impact of an Online Physician Group-Coaching Program to Improve Burnout and Self-Compassion in Trainees. Journal of Healthcare Management. 2024;69:414\u201323.\n
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\n26. Hsu C-L, Liu C-H, Huang C-C, Chen H-L, Chiu Y-L, Yang C-W. The effectiveness of online educational interventions on impostor syndrome and burnout among medical trainees: a systematic review. BMC Medical Education. 2024;24.\n
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\n27. Baumann N, Faulk C, Vanderlan J, Chen J, Bhayani RK. Small-Group Discussion Sessions on Imposter Syndrome. MedEdPORTAL. 2020. https://doi.org/10.15766/mep_2374-8265.11004.\n
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\n28. Mak KKL, Kleitman S, Abbott MJ. Impostor Phenomenon Measurement Scales: A Systematic Review. Frontiers in Psychology. 2019;10.\n
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Wiederverwendung

CC BY 4.0

Zitat

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@misc{friederichs2026,\n  author = {Friederichs, Hendrik},\n  title = {Das Impostor-Ph\u00e4nomen \u2013 was mache ich hier?},\n  date = {2026-09-10},\n  url = {https://medical-education.pages.ub.uni-bielefeld.de/research/mes-blog/posts/2026-09-10-impostor/},\n  doi = { 10.59350/0vw9m-k3092},\n  langid = {de}\n}\n
Bitte zitieren Sie diese Arbeit als:
\n1. Friederichs H. Das\nImpostor-Ph\u00e4nomen \u2013 was mache ich hier? 2026.\n
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Der Gedanke in der ersten Woche Die allererste Vorlesung.","tags":["Studierende","Studienstart","Wohlbefinden","Lernen"],"title":"Das Impostor-Ph\u00e4nomen \u2013 was mache ich hier?","updated_at":1789025415,"url":"https://medical-education.pages.ub.uni-bielefeld.de/research/mes-blog/posts/2026-09-10-impostor/","version":"v1"}],"out_of":55760,"page":1,"per_page":10,"total-results":55760}