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A highly stable N-heterocyclic carbene complex of trichloro-oxo-vanadium(V) displaying novel Cl-Ccarbene bonding interactions

Abernethy, C.D. and Codd, G.M. and Spicer, M.D. and Taylor, M.K. (2003) A highly stable N-heterocyclic carbene complex of trichloro-oxo-vanadium(V) displaying novel Cl-Ccarbene bonding interactions. Journal of the American Chemical Society, 125 (5). pp. 1128-1129. ISSN 0002-7863

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Abstract

Reaction of 1,3-dimesitylimidazol-2-ylidene and trichloro-oxo-vanadium(V) yields an air stable 1:1 adduct, which demonstrates the utility of N-heterocyclic carbenes to stabilize metal complexes in high oxidation states. The molecular structure of this compound reveals that the chloride ligands cis to the carbene are oriented toward the Ccarbene atom. Density functional theory calculations show that a bonding interaction occurs between lone pairs of these chlorides and the formally unoccupied p-orbital of the carbene. Previous studies indicated that this orbital was not involved in the bonding of N-heterocyclic carbenes to transition metals. The observed interaction therefore represents a new bonding mode for these widely used ligands.