Ultrafast photogeneration of a metal–organic nitrene from 1,1′-diazidoferrocene†
‡a
Markus
Bauer‡,
b
Luis I.
Domenianni,
b
Jonas
Schmidt,
b
Biprajit
Sarkar,
*cd
Peter
Vöhringer
*b
and
Vera
Krewald
*a
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.
- This article is part of the themed collections: 2024 Chemical Science HOT Article Collection, 2024 Chemical Science Covers and 2024 ChemSci Pick of the Week Collection
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