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Electrochemical oxidation and protonation of a bridging amide ligand at a dinuclear metal-sulfur site

Abstract : The electrochemical oxidation of the amide complex [Mo2(cp)2(μ-SMe)3(μ-NH2)] 1 (cp = η5-C5H5) has been investigated in tetrahydrofuran (thf) and MeCN electrolytes by cyclic voltammetry, controlled-potential electrolysis and coulometry. The two-electron oxidation of 1 leads to the release of a proton and to the formation of the imide derivative [Mo2(cp)2(μ-SMe)3(μ-NH)]+ 2. In MeCN, this reaction is reversible. The protonation of 1 has been shown to produce a complex in which a NH3 ligand is bound to a Mo centre; the protonated complex is stabilized by co-ordination of the anion of the acid, of the solvent or of a substrate to the neighbouring metal centre. The protonation performed in thf in the presence of chloride produces [Mo2(cp)2(μ-SMe)3(μ-Cl)] which is the precursor of the amide complex 1. The final protonation product formed in MeCN is [Mo2(cp)2(μ-SMe)3(MeCN)2]+, which also is a precursor of 1. Therefore, these experiments allow the construction of a hydrazine disproportionation cycle.
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https://hal.univ-brest.fr/hal-01770532
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Submitted on : Thursday, April 19, 2018 - 10:10:04 AM
Last modification on : Thursday, October 3, 2019 - 8:50:02 AM

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François Pétillon, Philippe Schollhammer, Jean Talarmin. Electrochemical oxidation and protonation of a bridging amide ligand at a dinuclear metal-sulfur site. Journal of the Chemical Society - Dalton Transactions, 1997, pp.4019--4024. ⟨hal-01770532⟩

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