H2NO^.自由基和顺-2-丁烯反应机理的理论研究  

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

作　　者：石国升[1] 丁益宏[1] 

机构地区：[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

出　　处：《高等学校化学学报》2009年第2期382-386,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:20103003;20573046;20773054);教育部博士点基金(批准号:200701830128);吉林省杰出青年基金(批准号:20050103);教育部新世纪优秀人才支持计划(NCET)资助

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.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 （abstraction-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 present results are expected to provide useful information for understanding the selective oxidation of unsaturated hydrocarbons by such type of oxygen-mediated radicals.

关 键 词：H2NO· 顺-2-丁烯 势能面 反应机理 

分 类 号：O641[理学—物理化学]