Theoretical Study on the Reaction of Et<sub>3</sub>GeCH=CH<sub>2</sub> with Et<sub>3</sub>SiOH

Abstract

The reaction of Et3GeCH=CH2 + Et3SiOH → Et3SiO–Ge–Et3 + CH2=CH2 has been studied using quantum chemistry methods. Geometries of reactants, transition states, and products have been optimized respectively at the b3lyp/6-311+g(2d,2p) level. The rate constants were evaluated using canonical variational transition state theory (CVT) and canonical variational transition state theory with small-curvaturetunneling contributions (CVT/SCT) over the temperature range of 200-3500K. The CVT/SCT rate constants exhibit typical non-Arrhenius behavior, and a three-parameter rate-temperature formula has been fitted as follows: k(T)=1.43×10-38T 5.41exp(-13200/T) (in units of cm3 molecule-1s-1).