取代基对有机金属铼化合物中分子内α-氢转移反应势垒的影响  

Effects of Substituents on the Reaction Barriers of the Intramolecular α-Hydrogen Transfer in Organometallic Rhenium Complexes

作　　者：王福冬[1] 高坤[1] 王长生[1] 

机构地区：[1]辽宁师范大学化学化工学院,大连116029

出　　处：《化学学报》2007年第20期2211-2216,共6页Acta Chimica Sinica

基　　金：国家自然科学基金(No.20573049);辽宁省科学技术基金(No.2004C019)资助项目.

摘　　要：使用B3LYP方法研究了有机铼化合物R3R5(NHR4)Re(=CHR1)(=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.R1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.R2为H时,α-氢转移反应势垒最低.R3和R5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.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.

关 键 词：金属铼有机化合物 α-氢转移反应 密度泛函理论 

分 类 号：O621.2[理学—有机化学]