Electrochemical Reduction of Nitrogenous Ligands at a Conserved Dinuclear Metal−Sulfur Site: Cleavage of the NN 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.
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Submitted on : Monday, May 13, 2019 - 11:29:08 AM
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François Pétillon, Philippe Schollhammer, Jean Talarmin, Kenneth Muir. Electrochemical Reduction of Nitrogenous Ligands at a Conserved Dinuclear Metal−Sulfur Site: Cleavage of the NN Bond of Phenyldiazene and Reduction of an Imide to NH 3. Inorganic Chemistry, American Chemical Society, 1999, 38 (9), pp.1954-1955. ⟨10.1021/ic9813359⟩. ⟨hal-02127137⟩

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