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Vibrational characterization of a diiron bridging hydride complex – a model for hydrogen catalysis

Gee, Leland B.; Pelmenschikov, Vladimir; Wang, Hongxin; Mishra, Nakul; Liu, Yu-Chiao; Yoda, Yoshitaka; Tamasaku, Kenji; Chiang, Ming-Hsi; Cramer, Stephen P.

FG Theoretische Chemie - Quantenchemie

A diiron complex containing a bridging hydride and a protonated terminal thiolate of the form [(μ,κ2-bdtH)(μ-PPh2)(μ-H)Fe2(CO)5]+ has been investigated through 57Fe nuclear resonance vibrational spectroscopy (NRVS) and interpreted using density functional theory (DFT) calculations. We report the Fe–μH–Fe wagging mode, and indications for Fe–μD stretching vibrations in the D-isotopologue, observed by 57Fe-NRVS. Our combined approach demonstrates an asymmetric sharing of the hydride between the two iron sites that yields two nondegenerate Fe–μH/D stretching vibrations. The studied complex provides an important model relevant to biological hydrogen catalysis intermediates. The complex mimics proposals for the binuclear metal sites in [FeFe] and [NiFe] hydrogenases. It is also an appealing prototype for the ‘Janus intermediate’ of nitrogenase, which has been proposed to contain two bridging Fe–H–Fe hydrides and two protonated sulfurs at the FeMo-cofactor. The significance of observing indirect effects of the bridging hydride, as well as obstacles in its direct observation, is discussed in the context of biological hydrogen intermediates.