title: A Theoretical Study of the Epoxidation of Olefins by Peracids.
abstract: For the parent reacting system, HCOOOH + CH(2)=CH(2) --> HCOOH + ethylene oxide, the overall potential energy surface has been determined using ab initio methods. The oxygen-addition transition state is found to be remarkably similar to that deduced experimentally. The O-H bond is retained in the transition state. Reasonable kinetic isotopic effects are obtained theoretically. The transition state leads to an unprecedented transient intermediate. That intermediate is converted to a hydrogen-bonded system between ethylene oxide and formic acid. Substituent effects on transition-state geometries are small, but the effects on activation energies are large.
authors.affiliation: Department of Chemistry, Nara University of Education, Takabatake-cho, Nara 630, Japan, and Institute for Natural Science, Nara University, 1500 Misasagi-cho, Nara 631, Japan.
authors.forename: Shinichi
authors.initials: S
authors.lastname: Yamabe
authors.forename: Chisako
authors.initials: C
authors.lastname: Kondou
authors.forename: Tsutomu
authors.initials: T
authors.lastname: Minato