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Updated: Feb 11, 2026

Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
Published on: June 8, 2022
An S = 1/2 Iron Complex Featuring N2, Thiolate, and Hydride Ligands: Reductive Elimination of H2 and Relevant
Nina X Gu1, Paul H Oyala1, Jonas C Peters1
1Division of Chemistry and Chemical Engineering , California Institute of Technology , Pasadena , California 91125 , United States.
Abstract:
Believed to accumulate on the Fe sites of the FeMo-cofactor (FeMoco) of MoFe-nitrogenase under turnover, strongly donating hydrides have been proposed to facilitate N2 binding to Fe and may also participate in the hydrogen evolution process concomitant to nitrogen fixation. Here, we report the synthesis and characterization of a thiolate-coordinated FeIII(H)(N2) complex, which releases H2 upon warming to yield an FeII-N2-FeII complex. Bimolecular reductive elimination of H2 from metal hydrides is pertinent to the hydrogen evolution processes of both enzymes and electrocatalysts, but well-defined examples are uncommon and usually observed from diamagnetic second- and third-row transition metals. Kinetic data obtained on the HER of this ferric hydride species are consistent with a bimolecular reductive elimination pathway, arising from cleavage of the Fe-H bond with a computationally determined BDFE of 55.6 kcal/mol.
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