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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (20): 2211-2216. 上一篇    下一篇

研究论文

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

王福冬，高坤，王长生*   

  1. (辽宁师范大学化学化工学院 大连 116029)
  • 投稿日期:2007-02-03 修回日期:2007-05-09 发布日期:2007-10-28
  • 通讯作者: 王长生

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

WANG Fu-Dong; GAO Kun; WANG Chang-Sheng*   

  1. (Department of Chemistry, Liaoning Normal University, Dalian 116029)
  • Received:2007-02-03 Revised:2007-05-09 Published:2007-10-28

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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.

关键词: 金属铼有机化合物, &alpha, -氢转移反应

The theoretical calculations on a series of intramolecular α-hydrogen transfer reactions in organometallic rhenium complexes R3R5(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 R2. For R3 and R4, the most suitable groups are silyl and t-butyl groups, respectively. Calculation results also show that additivity exists for the effects of substituents on the barriers of the α-hydrogen transfer reactions.

Key words: organometallic rhenium complex, α-hydrogen transfer reaction, density functional theory