Abernethy Colin D, Codd Gareth M, Spicer Mark D, Taylor Michelle K
Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, Scotland G1 1XL, United Kingdom.
J Am Chem Soc. 2003 Feb 5;125(5):1128-9. doi: 10.1021/ja0276321.
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.
1,3 - 二甲基咪唑 - 2 - 亚基与三氯氧钒（V）反应生成一种空气稳定的1:1加合物，这证明了N - 杂环卡宾在稳定高氧化态金属配合物方面的效用。该化合物的分子结构表明，与卡宾顺式的氯配体朝向卡宾碳原子定向。密度泛函理论计算表明，这些氯原子的孤对与卡宾形式上未占据的p轨道之间发生键合相互作用。先前的研究表明，该轨道不参与N - 杂环卡宾与过渡金属的键合。因此，观察到的这种相互作用代表了这些广泛使用的配体的一种新的键合模式。
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