几种无机碱金属盐作催化剂的醛的硅腈化反应机理的初步研究.docVIP

  几种无机碱金属盐作催化剂的醛的硅腈化 反应机理的初步研究# 苏志珊，李唯一，胡常伟** 5 10 15 20 25 30 35 40 （四川大学化学学院绿色化学与技术教育部重点实验室， 成都， 610064） 摘要：在 B3P86/6-31G*水平下, 研究了几种无机碱金属盐催化剂作用下 H3SiCN 与甲醛之间 的硅腈化反应机理。计算结果表明，无催化剂存在时，反应为协同机理，通过一四元环状过 渡态生成目标产物氰醇硅醚。气相反应能垒高达 38.0 kcal/mol。在催化剂作用下，反应涉及 六配位 Si 中间体的形成。碱金属盐催化剂通过羰基 O 原子与 H3SiCN 中 Si 原子的配位有效 活化了 Si-C 键。在 KHCO3 催化下，Si-C 键断裂及 C-C 键生成是协同过程；而在 LiHCO3 和 NaHCO3 催化下则是分步完成的。计算给出几种无机碱金属盐催化下反应速率控制步骤的 能垒大小顺序为：?E LiHCO3 (12.7 kcal/mol) ?E NaHCO3 (8.7 kcal/mol)?E KHCO3 (7.4 kcal/mol)。KHCO3 中 HCO3 部分所带负电荷更多，亲核性更强，因而对羰基底物活化能力更 强。 关键词：理论计算；碱金属盐；硅腈化；反应机理；醛 中图分类号：0643 Theoretical investigation on the mechanism of aldehyde cyanosilylation catalyzed by several inorganic salts SU Zhishan, LI Weiyi, HU Changwei (Key Laboratory of Green Chemistry Technology Ministry of Education, College of Chemistry, Sichuan Universit, Chengdu 610064) Abstract: The mechanism of cyanosilylation reaction of aldehyde catalyzed by several inorganic salts were investigated at the B3P86/6-31G* level. Calculations indicate that the non-catalyzed reaction proceeds concertedly via a four-membered-ring transition state, with the energy barrier of 38.0 kcal/mol in gas phase. The catalytic reactions involve the formation of hexacoordinate hypervalent silicate intermediates, in which the Si-C bond of H3SiCN is activated by coordinating O atom of carboxylic salts to Si atom of H3SiCN. The concerted mechanism involving the breaking of Si-C bond followed by C-C bond formation is adopted for the reaction catalyzed by KHCO3; while they occured stepwisely with NaHCO3 and LiHCO3 catalysts. The energy barriers for rate-determining step are predicted in the following order: ?E LiHCO3 (12.7 kcal/mol) ?E NaHCO3 (8.7 kcal/mol)?E KHCO3 (7.4 kcal/mol).The charge acculmulated on HCO3 moiety may be responsible for the high catalitic ability of KHCO3. Key words: Theroretical investigation; inorganic and organic salts; cyanosilylation; reaction mechanism; aldehyde 0 引言 醛与三甲基硅氰的加成反应是制备氰醇化合物的一类重要的方法，反应广泛采用金属络 合物作为催化剂[1-