Scherz, Frederik ; Bauer, Markus ; Domenianni, Luis I. ; Hoyer, Carolin ; Schmidt, Jonas ; Sarkar, Biprajit ; Vöhringer, Peter ; Krewald, Vera (2024)
Ultrafast photogeneration of a metal–organic nitrene from 1,1′-diazidoferrocene.
In: Chemical Science, 2024, 15 (18)
doi: 10.26083/tuprints-00027350
Artikel, Zweitveröffentlichung, Verlagsversion
 | Es ist eine neuere Version dieses Eintrags verfügbar. |
Kurzbeschreibung (Abstract)
Ferrocene and its derivatives have fascinated chemists for more than 70 years, not least due to the analogies with the properties of benzene. Despite these similarities, the obvious difference between benzene and ferrocene is the presence of an iron ion and hence the availability of d-orbitals for properties and reactivity. Phenylnitrene with its rich photochemistry can be considered an analogue of nitrenoferrocene. As with most organic and inorganic nitrenes, nitrenoferrocene can be obtained by irradiating the azide precursor. We study the photophysical and photochemical processes of dinitrogen release from 1,1′-diazidoferrocene to form 1-azido-1′-nitrenoferrocene with UV-pump–mid-IR-probe transient absorption spectroscopy and time-dependent density functional theory calculations including spin–orbit coupling. An intermediate with a bent azide moiety is identified that is pre-organised for dinitrogen release via a low-lying transition state. The photochemical decay paths on the singlet and triplet surfaces including the importance of spin–orbit coupling are discussed. We compare our findings with the processes discussed for photochemical dinitrogen activation and highlight implications for the photochemistry of azides more generally.
| Typ des Eintrags: | Artikel |
|---|---|
| Erschienen: | 2024 |
| Autor(en): | Scherz, Frederik ; Bauer, Markus ; Domenianni, Luis I. ; Hoyer, Carolin ; Schmidt, Jonas ; Sarkar, Biprajit ; Vöhringer, Peter ; Krewald, Vera |
| Art des Eintrags: | Zweitveröffentlichung |
| Titel: | Ultrafast photogeneration of a metal–organic nitrene from 1,1′-diazidoferrocene |
| Sprache: | Englisch |
| Publikationsjahr: | 13 Mai 2024 |
| Ort: | Darmstadt |
| Publikationsdatum der Erstveröffentlichung: | 9 April 2024 |
| Ort der Erstveröffentlichung: | Cambridge |
| Verlag: | Royal Society of Chemistry |
| Titel der Zeitschrift, Zeitung oder Schriftenreihe: | Chemical Science |
| Jahrgang/Volume einer Zeitschrift: | 15 |
| (Heft-)Nummer: | 18 |
| DOI: | 10.26083/tuprints-00027350 |
| URL / URN: | https://tuprints.ulb.tu-darmstadt.de/27350 |
| Zugehörige Links: | |
| Herkunft: | Zweitveröffentlichung DeepGreen |
| Kurzbeschreibung (Abstract): | Ferrocene and its derivatives have fascinated chemists for more than 70 years, not least due to the analogies with the properties of benzene. Despite these similarities, the obvious difference between benzene and ferrocene is the presence of an iron ion and hence the availability of d-orbitals for properties and reactivity. Phenylnitrene with its rich photochemistry can be considered an analogue of nitrenoferrocene. As with most organic and inorganic nitrenes, nitrenoferrocene can be obtained by irradiating the azide precursor. We study the photophysical and photochemical processes of dinitrogen release from 1,1′-diazidoferrocene to form 1-azido-1′-nitrenoferrocene with UV-pump–mid-IR-probe transient absorption spectroscopy and time-dependent density functional theory calculations including spin–orbit coupling. An intermediate with a bent azide moiety is identified that is pre-organised for dinitrogen release via a low-lying transition state. The photochemical decay paths on the singlet and triplet surfaces including the importance of spin–orbit coupling are discussed. We compare our findings with the processes discussed for photochemical dinitrogen activation and highlight implications for the photochemistry of azides more generally. |
| Status: | Verlagsversion |
| URN: | urn:nbn:de:tuda-tuprints-273509 |
| Zusätzliche Informationen: | This article is part of the themed collections: 2024 Chemical Science HOT Article Collection, 2024 ChemSci Pick of the Week Collection and 2024 Chemical Science Covers |
| Sachgruppe der Dewey Dezimalklassifikatin (DDC): | 500 Naturwissenschaften und Mathematik > 540 Chemie |
| Fachbereich(e)/-gebiet(e): | 07 Fachbereich Chemie 07 Fachbereich Chemie > Quantenchemie |
| Hinterlegungsdatum: | 13 Mai 2024 13:24 |
| Letzte Änderung: | 14 Mai 2024 06:38 |
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- Ultrafast photogeneration of a metal–organic nitrene from 1,1′-diazidoferrocene. (deposited 13 Mai 2024 13:24) [Gegenwärtig angezeigt]
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