Reaction pathways of singlet silylene and singlet germylene with water, methanol, ethanol, dimethyl ether, and trifluoromethanol: An ab initio molecular orbital study
Mw. Heaven et al., Reaction pathways of singlet silylene and singlet germylene with water, methanol, ethanol, dimethyl ether, and trifluoromethanol: An ab initio molecular orbital study, J PHYS CH A, 105(7), 2001, pp. 1185-1196
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 id
entified two new reaction channels on each reaction surface, except for rea
ctions involving dimethyl ether. The previously unreported reaction channel
s involve H-2 elimination following the initial formation of an association
complex. For reactions involving singlet silylene and water, a simple acti
vated complex theory (ACT) analysis predicts that these newly identified re
action channels are equally likely to be accessed as the previously identif
ied 1,2 hydrogen atom shift channels. For reactions involving singlet germy
lene and water, a similar ACT analysis predicts that the H-2-elimination ch
annels will occur in preference to the 1,2 hydrogen shift. Indeed, the room
-temperature rate constants for H-2 elimination from the germanium complex
are predicted to be approximately 5 orders of magnitude greater than for th
e H atom migration channel.