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

J Chem Theory Comput. 2016 Jan 12;12(1):231-7. doi: 10.1021/acs.jctc.5b01100. Epub 2015 Dec 16.

Abstract

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.