First example of the formation of a Si–C bond from an intramolecular Si–H⋯H–C diyhydrogen interaction in a metallacarborane: A theoretical study

Abstract

The recently reported crystal structure of [NMe 4][1-SiMe 2H-3,3′-Co(1,2-C 2B 9H 10)(1′,2′-C 2B 9H 11)] shows short contacts between the Si–H proton acceptor group and the C c–H proton donor moiety in the dicarbollide ligand. These short contacts were studied within the framework of the Quantum Theory of Atoms in Molecules (QTAIM) at different levels of DFT theory (B3LYP/6-311(d,p) and BP86/TZ2P(+)) that shows the existence of a bifurcated Si–H⋯H–C c dihydrogen bond. This paper presents the study of an experimental uncommon Si–H group playing as proton acceptor bond in a dihydrogen bond where hydrides like M–H (M, as metal transition), B–H or Al–H usually perform this role. Furthermore, this paper accounts with a new simple method to estimate bonding energies for closed-shell intramolecular interactions in the scheme of Voronoi charge population analysis and Coulomb′s Law.