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Electrochemical dehydrodimerisation of a vinylenylamide ligand: Formation of the binuclear group Mo≡N+CH=CHCH=CHCH=CHN+≡Mo which displays very strong electronic coupling in the (MoIII)-(MoIV) mixed-valence state

Abstract : Electrochemical dehydrodimerisation of an _Mo-N=CHCH=CH2_ group gives an all-trans-_≡N+CH=CHCH=CHCH=CHN+≡_ ligand, bridging two MoIV centres; the ₍MoIII)-bridge-(MoIV)) mixed-valence state is accessible by electrochemical reduction and exhibits very strong electronic coupling over the 11.7 Å which separates the two metal centres; this accords with EHMO calculations which show that the SOMO has substantial (30%) bridging-ligand character; in its capacity to function as a molecular wire linking two metal centres, the eight-atom hexatriene di(imide) chain (N(CH)6NJ compares favourably with C8 chains of acetylenic carbons bridging other metal centres.
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https://hal.univ-brest.fr/hal-01770713
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Submitted on : Thursday, April 19, 2018 - 10:57:54 AM
Last modification on : Thursday, March 5, 2020 - 2:03:45 PM

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  • HAL Id : hal-01770713, version 1

Citation

Y. Alias, M.-L. Abasq, F. Barrière, S.C. Davies, S.A. Fairhurst, et al.. Electrochemical dehydrodimerisation of a vinylenylamide ligand: Formation of the binuclear group Mo≡N+CH=CHCH=CHCH=CHN+≡Mo which displays very strong electronic coupling in the (MoIII)-(MoIV) mixed-valence state. Chemical Communications, Royal Society of Chemistry, 1998, pp.675--676. ⟨hal-01770713⟩

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