The influence of a S-to-S bridge in diiron dithiolate models on the oxidation reaction: a mimic of the H airox state of [FeFe]-hydrogenases

Abstract

Two-electron oxidation of a diiron complex (1) containing a bulky S-to-S bridge with an exocyclic carbonyl group affords [1(OH)]⁺, which replicates the coordination structure and electronic configuration of H^air_ox, and the chemically reversible reaction between 1 and [1(OH)]⁺ mimics the bioprocess of interconversion of the inactive H^air_ox and the active H_red states of the [FeFe]-hydrogenases.