π Activation of Alkynes in Homogeneous and Heterogeneous Gold Catalysis
π Activation of Alkynes in Homogeneous and Heterogeneous Gold Catalysis
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DOI：
10.1021/acs.jpca.6b01037
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发表时间：
2016-07-14
影响因子：
2.9
通讯作者：
Tarantelli, Francesco
中科院分区：
文献类型：
--
作者：
Bistoni, Giovanni;Belanzoni, Paola;Tarantelli, Francesco
研究了炔烃在与金基催化剂（均相催化中常用的中性和带正电的金簇和金配合物）配位时对亲核攻击的活化，以阐明 Au-C 键的 sigma 供体和 pi 反向供体组分的作用（我们将乙炔视为原型底物）。电荷位移 (CD) 分析用于获得 sigma 捐赠和 pi 反馈的明确测量，并找出相应的电荷流如何影响经历亲核攻击的亲电碳上的电子密度。该信息用于合理化模型加氢胺化反应的亲核攻击步骤中一系列催化剂的活性。首次将 Dewar-Chat-Duncanson 模型的组成部分（捐赠和反捐赠）与化学反应的动力学参数进行定量关联。
The activation of alkynes toward nucleophilic attack upon coordination to gold-based catalysts (neutral and positively charged gold clusters and gold complexes commonly used in homogeneous catalysis) is investigated to elucidate the role of the sigma donation and pi back-donation components of the Au-C bond (where we consider ethyne as prototype substrate). Charge displacement (CD) analysis is used to obtain a well-defined measure of sigma donation and pi back-donation and to find out how the corresponding charge flows affect the electron density at the electrophilic carbon undergoing the nucleophilic attack. This information is used to rationalize the activity of a series of catalysts in the nucleophilic attack step of a model hydroamination reaction. For the first time, the components of the Dewar-Chatt-Duncanson model, donation and back-donation, are put in quantitative correlation with the kinetic parameters of a chemical reaction.