中文摘要：

使用B3LYP方法研究了有机铼化合物R^3R^5（NHR4）Re（=CHR^1）（=NR2）中分子内α-氢转移反应，探讨了不同取代基对α-氢转移反应势垒的影响．研究发现，可以通过改变取代基来影响过渡金属Re有机化合物中的α-氢转移反应．R^1位置的取代基为Me或CMe3时，可以较大程度降低α-氢转移反应的势垒．R^2为H时，α-氢转移反应势垒最低．R^3和R^5位置为SiH3时的反应势垒最低．R4为CMe3时，α-氢转移反应势垒最低．研究结果还表明，取代基对于反应势垒的影响有加和性．

英文摘要：

The theoretical calculations on a series of intramolecular a-hydrogen transfer reactions in organometallic rhenium complexes RaRS（NHR4）Re（：CHR1）（：NR2） were carried out with B3LYP method and the effects of substituents on the barriers of the α-hydrogen transfer reactions were explored. It was found that the most preferable substituents are methyl or t-butyl groups for R1 while the hydrogen atom is the best one for RE. For R3 and R4, the most suitable groups are silyl and t-butyl groups, respectively. Calcu- lation results also show that additivity exists for the effects of substituents on the barriers of the α-hydrogen transfer reactions.