高等学校化学学报

高等学校化学学报

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H2NO·自由基和顺-2-丁烯反应机理的理论研究

石国升, 丁益宏   

  1. 吉林大学理论化学研究所, 理论化学计算国家重点实验室, 长春 130023
  • 收稿日期:2007-12-27 修回日期:1900-01-01 出版日期:2009-02-10 发布日期:2009-02-10
  • 通讯作者: 丁益宏

Theoretic Studies on the Reaction Mechanism Between H2NO· Radicals and cis-2-Butene

SHI Guo-Sheng, DING Yi-Hong*   

  1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China
  • Received:2007-12-27 Revised:1900-01-01 Online:2009-02-10 Published:2009-02-10
  • Contact: DING Yi-Hong

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摘要： 采用UB3LYP/6-311++G(d,p)//UB3LYP/6-31G(d)方法对H2NO·自由基和顺-2-丁烯反应的势能面进行了研究, 发现了三类共5条可能的反应通道: L4-Ⅰ和L4-Ⅱ(夺氢-加成), L4-Ⅲ和L4-Ⅳ(加成-加成-消除), L4-Ⅴ(加成-加成-消除-催化转换). 动力学分析表明, 该反应为加成-加成-消除过程.

关键词: H2NO·, 顺-2-丁烯, 势能面, 反应机理

Abstract: Nitroxyl(>NO·) radicals have received considerable attention due to their importance in various fields, e.g., combustion, organic synthesis, biological systems. In this paper, the UB3LYP/6-311++G(d,p)//UB3LYP/6-31G(d) study was performed on the complex reaction potential energy surfaces of H2NO· radicals with cis-2-butene with an attempt to understand the possible reaction mechanism. Three types, five distinct elementary channels were revealed as: L4-Ⅰ and L4-Ⅱ(ion-addition), L4-Ⅲ and L4-Ⅳ(addition-addition-elimination), L4-Ⅴ(addition-addition-elimination-catalyzed conversion). The kinetic analysis demonstrated that the title reaction undergoes the addition-addition-elimination mechanism(L4-Ⅳ). The pre-sent results are expected to provide useful information for understanding the selective oxidation of unsaturated hydrocarbons by such type of oxygen-mediated radicals.

Key words: H2NO·, cis-2-Butene, Potential energy surface, Reaction mechanism

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