(Cl-nacnac)Pt(H)与端炔的反应机理.PDFVIP

物理化学学报(Wuli Huaxue Xuebao) March Acta Phys. ⁃Chim. Sin. 2011, 27 (3), 571-576 571 [Article] (Cl-nacnac)Pt(H)与端炔的反应机理 王家勇 毕思玮* 赵俊凤 ( 曲阜师范大学化学与化工学院, 山东曲阜273165) 摘要: 在Templeton 实验(West, N. M.; et al. Organometallics 2008, 27, 5252)的基础上, 利用密度泛函理论 研究了(Cl-nacnac)Pt(H)(Cl-nacnac: bis(N-aryl)-β-diiminate)与端炔的主、副反应机理. 结果表明: 叔丁基乙炔 以1,2-方式插入到Pt―H键之间生成主产物, C―C 键生成为决速步骤; 以2,1-方式插入到Pt―H键之间生成副 产物, 炔烃插入为决速步骤. 基于主、副反应机理, 合理地解释了主、副产物生成的原因. 分析表明, 主产物是热 力学控制的产物, 而副产物是动力学控制的产物. 关键词: 密度泛函理论; 反应机理; 铂; 炔烃插入; 炔烃双聚 中图分类号: O641 Reaction Mechanisms between (Cl-nacnac)Pt(H) and a Terminal Alkyne WANG Jia-Yong BI Si-Wei* ZHAO Jun-Feng (School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, Shandong Province, P. R. China) Abstract: On the basis of Templeton ′s experiment (West, N. M.; et al. Organometallics 2008, 27, 5252), the mechanisms of the main and the side reactions between (Cl-nacnac)Pt(H) (Cl-nacnac: bis(N-aryl)- β-diiminate) and a terminal alkyne were investigated by density functional theory. Our study shows that the 1,2-insertion of t-BuC≡CH into the Pt ―H bond generates the main products and that C ―C bond formation is the rate-determining step. The 2,1-insertion of t-BuC≡CH into the Pt ―H bond generates the by- products and alkyne insertion is the rate-determining step. Based on the mechanisms of the main and side reactions the presence of the main product and the by-product could be explained. We found that the main product is thermod