Density Functional Study of Some Germylene Insertion Reactions

Abstract

Complete geometry optimizations were carried out using density functional theory to study potential energy surfaces for the insertion of germylene into C−H bonds of methane. The GeXY + CH4 (GeXY = GeH2, GeCH2, GeH(CH3), Ge(CH3)2, GeHF, GeF2, GeHCl, GeCl2, GeHBr, and GeBr2) systems are the subject of the present study. All the stationary points were determined at the B3LYP/6-311G* level of theory. Our theoretical findings suggest that the computed structures of germylenes are in good agreement with the available experimental results, with the bond lengths and angles in agreement to within 0.04 A and 1.0°, respectively. A configuration mixing model based on the theory of Pross and Shaik has been used to develop an explanation for the barrier height as well as the reaction enthalpy. Our theoretical findings suggest that the singlet−triplet splitting (ΔEst = Etriplet − Esinglet) of the GeXY species can be used as a guide to predict its activity for insertion reactions. Thus, the major conclusion that can be d...