London Dispersion Decisively Contributes to the Thermodynamic Stability of Bulky NHC-Coordinated Main Group Compounds

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• 作者：J. Philipp Wagner ; Peter R. Schreiner
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2016
• 出版时间：January 12, 2016
• 年：2016
• 卷：12
• 期：1
• 页码：231-237
• 全文大小：431K
• ISSN：1549-9626

文摘

We evaluated the dispersion stabilization of a series of seemingly reactive main group compounds coordinated to bulky N-heterocyclic carbene ligands. We computed the thermochemistry of hypothetical isodesmic exchange reactions of these ligands with their unsubstituted parent systems employing the B3LYP/6-311G(d,p) level of theory with and without dispersion corrections. The energy difference between these two approaches gave dispersion corrections of 30 kcal mol^–1 and more. We therefore conclude that London dispersion contributes critically to the thermodynamic stabilities of these compounds. As such, these core–shell structures undergo reactions of the reactive core as long as the dispersion stabilization is conserved.