An ab-initio study of some homolytic substitution reactions of acyl radicals at silicon, germanium and tin

Abstract

Ab initio calculations using the 6-311G**, cc-pVDZ, and (valence) double-ζ pseudopotential (DZP) basis sets, with (MP2, QCISD, CCSD(T)) and without (UHF) the inclusion of electron correlation, and density functional (BHandHLYP, B3LYP) calculations predict that homolytic substitution reactions of acetyl radicals at the silicon atoms in disilane can proceed via both backside and frontside attack mechanisms. At the highest level of theory (CCSD(T)/cc-pVDZ//MP2/cc-pVDZ), energy barriers (ΔE^‡) of 77.2 and 81.9 kJ mol⁻¹ are calculated for the backside and frontside reactions respectively. Similar results are obtained for reactions involving germanium and tin with energy barriers (ΔE^‡) of 53.7–84.2, and 55.0–89.7 kJ mol⁻¹ for the backside and frontside mechanisms, respectively. These data suggest that both homolytic substitution mechanisms are feasible for homolytic substitution reactions of acetyl radicals at silicon, germanium, and tin. BHandHLYP calculations provide geometries and energy barriers for backside and frontside transition states in good agreement with those obtained by traditional ab initio techniques.