Theoretical Studies On α-Hydrogen Transfer Reactions Of Organometallic Rhenium Complexes

Based on density functional theory (DFT) and B3LYP method,we made a theoretical study of theα?hydrogen transfer reaction system involving organometallic rhenium complexes R3R3′(NHR4)Re (=CHR1)(=NR2)。We studied the mechanism of each reaction。We optimized the structure of the reactants,products and transition states,and calculated the energies and frequencies of each conformers。Chapter one mainly deals with a seriesα?hydrogen shift reactions in organometallic rhenium complexes R3R3′(NHR4)Re (=CHR1)(=NR2)。The purpose is to find out the most preferable substituents that can lower the activity energy to a largest extent。It is found that the most preferable substituents are methyl or t-butyl groups for position R1 while the hydrogen atom is the best one for position R2。For positions R3 and R4,the most suitable groups are silyl and t?butyl groups,respectively。Calculation results also show that the additive properly exists for the effects of substituents on the reaction barriers of theα?hydrogen transfer reactions。In the second chapter,we mainly deals with a seriesα?hydrogen shift reactions,and studies the isomerization reaction of organometallic rhenium complexes。...