Electrochemical Reduction of Nitrogenous Ligands at a Conserved Dinuclear Metal-Sulfur Site: Cleavage of the N=N Bond of Phenyldiazene and Reduction of an Imide to NH(3).

Abstract

The electrochemical reduction of the phenyldiazene complex [Mo2(cp)2(μ-SMe)3(μ-η2-HNNPh)]+ in the presence of HX (X = TsO, CF3CO2) produces aniline and an ammino derivative. This may involve [Mo2(cp)2(μ-SMe)3(μ-NH)]+ as an intermediate since the imide complex also reduces to the ammino derivative in the presence of HX. These electrochemical steps complete a cycle whereby a phenyldiazenido ligand coordinated to the {Mo2(cp)2(μ-SMe)3+} core is cleaved to PhNH2 and NH3 by successive proton- and electron-transfer steps.