Understanding Homolytic Translocation Chemistry—An Ab Initio Study of Some 1,5-Transfers of Silyl, Germyl and Stannyl Groups of Synthetic Significance

Abstract

Ab initio molecular orbital and density functional calculations predict that 1,5-homolytic translocation reactions involving silyl, germyl and stannyl groups between two alkyl carbon atoms, between alkoxy oxygen atoms, and between alkyl and allylic carbon atoms proceed via concerted mechanisms involving frontside substitution at the higher heteroatom involved; CCSD(T)/DZP//B3LYP/DZP calculations predict energy barriers ranging from 69 to 114 kJ mol^–1 depending on the system involved.