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 - Université de Bretagne Occidentale Access content directly
Journal Articles Chemical Communications Year : 1998

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

Y. Alias
  • Function : Author
M.-L. Abasq
  • Function : Author
  • PersonId : 946836
F. Barrière
S.C. Davies
  • Function : Author
S.A. Fairhurst
  • Function : Author
D.L. Hughes
  • Function : Author
S.K. Ibrahim
  • Function : Author
C.J. Pickett
  • Function : Author

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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Dates and versions

hal-01770713 , version 1 (19-04-2018)

Identifiers

  • HAL Id : hal-01770713 , version 1

Cite

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, 1998, pp.675--676. ⟨hal-01770713⟩
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