Issue 18, 2024

Ultrafast photogeneration of a metal–organic nitrene from 1,1′-diazidoferrocene

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.

Graphical abstract: Ultrafast photogeneration of a metal–organic nitrene from 1,1′-diazidoferrocene

Supplementary files

Article information

Article type
Edge Article
Submitted
05 Feb 2024
Accepted
08 Apr 2024
First published
09 Apr 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 6707-6715

Ultrafast photogeneration of a metal–organic nitrene from 1,1′-diazidoferrocene

F. Scherz‡, M. Bauer‡, L. I. Domenianni, C. Hoyer, J. Schmidt, B. Sarkar, P. Vöhringer and V. Krewald, Chem. Sci., 2024, 15, 6707 DOI: 10.1039/D4SC00883A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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