Reaction Pathways of Singlet Silylene and Singlet Germylene with Water, Methanol, Ethanol, Dimethyl Ether, and Trifluoromethanol: An ab Initio Molecular Orbital Study

Abstract

Ab initio molecular orbital calculations have been performed to explore the reaction potential energy surfaces of singlet silylene and germylene with water, methanol, ethanol, dimethyl ether, and trifluoromethanol. We have identified two new reaction channels on each reaction surface, except for reactions involving dimethyl ether. The previously unreported reaction channels involve H2 elimination following the initial formation of an association complex. For reactions involving singlet silylene and water, a simple activated complex theory (ACT) analysis predicts that these newly identified reaction channels are equally likely to be accessed as the previously identified 1,2 hydrogen atom shift channels. For reactions involving singlet germylene and water, a similar ACT analysis predicts that the H2-elimination channels will occur in preference to the 1,2 hydrogen shift. Indeed, the room-temperature rate constants for H2 elimination from the germanium complex are predicted to be approximately 5 orders of ma...