(Cl-nacnac)Pt(H)与端炔的反应机理

引用本文: 王家勇, 毕思玮, 赵俊凤. (Cl-nacnac)Pt(H)与端炔的反应机理[J]. 物理化学学报, 2011, 27(03): 571-576. doi: 10.3866/PKU.WHXB20110312 shu

Citation: WANG Jia-Yong, BI Si-Wei, ZHAO Jun-Feng. Reaction Mechanisms between (Cl-nacnac)Pt(H) and a Terminal Alkyne[J]. Acta Physico-Chimica Sinica, 2011, 27(03): 571-576. doi: 10.3866/PKU.WHXB20110312 shu

(Cl-nacnac)Pt(H)与端炔的反应机理

基金项目:
山东省自然科学基金(Y2007B23) (Y2007B23)

固体表面物理化学国家重点实验室(厦门大学)(200702)资助项目 (厦门大学)(200702)

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:

English

Reaction Mechanisms between (Cl-nacnac)Pt(H) and a Terminal Alkyne

1.
School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, Shandong Province, P. R. China
Received Date: 27 October 2010
Available Online: 03 March 2011
Fund Project:
山东省自然科学基金(Y2007B23)

固体表面物理化学国家重点实验室(厦门大学)(200702)资助项目

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 thermodynamically controlled while the side product is kinetically controlled.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

(Cl-nacnac)Pt(H)与端炔的反应机理

English

Reaction Mechanisms between (Cl-nacnac)Pt(H) and a Terminal Alkyne

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中国化学会秘书处

(Cl-nacnac)Pt(H)与端炔的反应机理

English

Reaction Mechanisms between (Cl-nacnac)Pt(H) and a Terminal Alkyne

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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