The extreme π-loading pincer N-heterocyclic carbene Ta(V)-bis(imido) complex showed high activity in catalytic reaction of amino-alkene (2,2-diphenylpent-4-en-1-amine). Pathways for the generation of cyclic imine product form oxidative amination, formation of the reduced substrate, generation of cyclic amine product from hydroamination, and dehydrogenation of hydroamination product were proposed using density functional theory (DFT) computations. Multiple pathways for the generation of oxidative amination product were proposed. The lowest activation energy of the rate-determining step during the generation of cyclic imine product form oxidative amination was 15.5 kcal/mol. The relative activation energies of the rate-determining step for the generations of reduction product and hydroamination product were 26.8 kcal/mol and 24.4 kcal/mol, respectively. High temperature was significantly favorable in the formation of cyclic imine from oxidative amination, and also promoted the conversion between the hydroamination product and the oxidative amination product. Computational results successfully explained the experimental observations.

Oxidative amination of alkene by extreme π-loading pincer N-heterocyclic carbene Tantalum bis(imido) complex

255th National Meeting (2018)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.