A mononuclear hexa-coordinated iron carbonyl complex [Fe(μ-bdt)(CO)(PTA)] 1 (bdt = 1,2-benzenedithiolate; PTA = 1,3,5-triaza-7-phosphaadamantane) with two bulky phosphine ligands in the trans position was synthesized and characterized by X-ray structural analysis coulometry data, FTIR, electrochemistry and electronic structure calculations. The complex undergoes a facilitated two-electron reduction 1/1 and shows an inverted one-electron reduction for 1/1 at higher potentials. Electrochemical investigations of 1 are compared to the closely related [Fe(bdt)(CO)(PMe)] compound. A mechanistic suggestion for the hydrogen evolution reaction upon proton reduction from acid media is derived. The stability of 1 in both weak and strong acids is monitored by cyclic voltammetry.
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