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Electrochemistry of molybdenum imides: Cleavage of molybdenum-nitrogen triple bonds to release ammonia or amines

Abstract : The electrochemical reduction of molybdenum(IV) alkylimides trans-[MoX(NR)(dppe)2]+ (X = halide, R = alkyl, dppe = Ph2PCH2CH2PPh2) proceeded by two pathways. In the absence of a source of protons, moderately stable five-co-ordinate molybdenum(II) imides are formed via an initial single-electron transfer followed by rate-determining loss of the trans-halide ligand and an additional electron transfer. In the presence of a source of protons, molybdenum-halide bond cleavage is intercepted by protonation at N which gives an amide intermediate. Further electron-transfer chemistry liberates amines and yields a dinitrogen complex in an overall four-electron process. Molybdenum(IV) imides trans-[MoX(NH)(dppe)2]+ were reduced to amide intermediates with the parent imide cation providing the source of protons and water probably acts as a proton-transfer relay. The amide has two fates; it is either converted into a nitride by hydrogen loss or, at a potential which encompasses its further reduction, yields ammonia and a dinitrogen complex.
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https://hal.univ-brest.fr/hal-01770533
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Submitted on : Thursday, April 19, 2018 - 10:10:05 AM
Last modification on : Thursday, November 29, 2018 - 4:09:11 PM

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Y. Alias, S.K. Ibrahim, M.A. Queiros, A. Fonseca, J. Talarmin, et al.. Electrochemistry of molybdenum imides: Cleavage of molybdenum-nitrogen triple bonds to release ammonia or amines. Journal of the Chemical Society - Dalton Transactions, 1997, pp.4807--4815. ⟨hal-01770533⟩

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