Study On Catalytic Mechanism Of Hydrogenation Of Hydrogenation To High - Valent Transition Metal Complexes

The rapid development of quantum chemistry provides a strong theoretical to support the study of organic reactions’ inner mechanism. The main content of this article is to use quantum chemical calculation methods to study the inner mechanism of carbonyl compounds’ hydrosilylation which is catalyzing by the transition metal complexes MoO2Cl2and (POCOP)IrH+. The main contents are as follows:The first chapter mainly introduces the primitive steps of the transition metal complexes to organic reactions and the mechanism of transition metal complexes catalysis of hydrosilylation.The second chapter simply introduces the calculation methods of quantum chemical.The third chapter and the fourth chapter describe the main research, which were accomplished during my Master’s Degree period.The third chapter mainly introduces the research of the mechanism of high-valent oxo-molybdenum MoO2Cl2catalyzing imine compounds’ hydrosilylation. By using the Gaussian09program package to calculate the free energy of all important states, and compare different pathway’s potential energy surface. The final result can be concluded that the optimal pathway is ionic hydrogenation pathway. This paper is published on Catalysis Science&Technology,2014,4,4-46.The fourth chapter mainly introduces the research of the mechanism of POCOP-Pincer Iridium(Ⅲ)(POCOP) IrH+catalyzing amide compounds’ hydrosilylation. By using the Gaussian09program package to calculate the free energy of all important states, and compare different pathway’s potential energy surface. The final result can be concluded that the optimal pathway is ionic hydrogenation pathway.These studies show the reliability of quantum computational methods in mechanistic studies of transition metal complexes mediated organic reactions. They are able to provide information that is difficult to gain from experimental.