title: Theoretical study of the mechanisms of palladation of methylenecyclopropane and [3 + 2] cycloadditions.
abstract: Palladation of methylenecyclopropane and [3 + 2] cycloaddition with alkenes have been studied theoretically. In palladium complexes of methylenecyclopropane or trimethylenemethane, the eta 2 forms have been shown to be more stable than the palladacyclobutane forms. However, the barrier heights to yield palladacyclobutanes are not very high and the methylene-bridged carbon can be converted to the metal-attached carbon on palladium via a ring-opened transition state, allowing the scrambling of hydrogens in methylenecyclopropane. With respect to the palladium-catalyzed [3 + 2] cycloaddition reaction of methylenecyclopropane with alkenes, the path via palladacyclobutanes has been demonstrated to be more favorable than the path via an eta 2 complex. These results are discussed by using the paired interaction orbital scheme.
authors.affiliation: Division of Molecular Engineering, Kyoto University, Kyoto 606-8501, Japan.
authors.forename: T
authors.initials: T
authors.lastname: Suzuki
authors.forename: H
authors.initials: H
authors.lastname: Fujimoto