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

C.D. Abernethy, G.M. Codd, M.D. Spicer, M.K. Taylor

Research output: Contribution to journalArticle

132 Citations (Scopus)

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.
LanguageEnglish
Pages1128-1129
Number of pages1
JournalJournal of the American Chemical Society
Volume125
Issue number5
DOIs
Publication statusPublished - 5 Feb 2003

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Vanadium
Ligands
Chlorides
Metal complexes
Molecular structure
Transition metals
Density functional theory
Coordination Complexes
Molecular Structure
Atoms
Oxidation
Metals
Air
carbene

Keywords

  • N-heterocyclic carbenes
  • Density functional theory
  • ligands

Cite this

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title = "A highly stable N-heterocyclic carbene complex of trichloro-oxo-vanadium(V) displaying novel Cl-Ccarbene bonding interactions",
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.",
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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.; Codd, G.M.; Spicer, M.D.; Taylor, M.K.

In: Journal of the American Chemical Society, Vol. 125, No. 5, 05.02.2003, p. 1128-1129.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A highly stable N-heterocyclic carbene complex of trichloro-oxo-vanadium(V) displaying novel Cl-Ccarbene bonding interactions

AU - Abernethy, C.D.

AU - Codd, G.M.

AU - Spicer, M.D.

AU - Taylor, M.K.

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AB - 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.

KW - N-heterocyclic carbenes

KW - Density functional theory

KW - ligands

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