Presented herein are detailed ^1/2H and ¹³C pulse EPR and DFT investigations of an S=1/2 terminal iron–carbene species. These studies reveal substantial spin density localized at the carbene-bound Fe center, in contrast with what has been reported to date for radical metal–carbenoid species. The {Fe=C(H)Ar}¹¹ complex serves as a well-defined reference compound for comparison to data reported for in situ trapped intermediates.

Abstract

We report the synthesis and spectroscopic characterization of a series of iron-carbene complexes in redox states {Fe=C(H)Ar}^10–11. Pulse EPR studies of the ^1,2H and ¹³C isotopologues of {Fe=C(H)Ar}¹¹ reveal the high covalency of the Fe–carbene bonding, leading to a more even spin distribution than commonly observed for reduced Fischer carbenes.

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Volume60, Issue52

December 20, 2021

Pages 27220-27224

Probing Redox Non-Innocence in Iron–Carbene Complexes {Fe=C(H)Ar}^10–11 by ^1,2H and ¹³C Pulse Electron Paramagnetic Resonance

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Probing Redox Non-Innocence in Iron–Carbene Complexes {Fe=C(H)Ar}10–11 by 1,2H and 13C Pulse Electron Paramagnetic Resonance

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Probing Redox Non-Innocence in Iron–Carbene Complexes {Fe=C(H)Ar}^10–11 by ^1,2H and ¹³C Pulse Electron Paramagnetic Resonance