金属碳,卡宾阳离子[M-X]+(M=Au,Ag,Cu;X=C,CH2)与甲烷反应机制研究

doi:10.7503/cjcu20170039

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (8): 1406.doi: 10.7503/cjcu20170039

金属碳,卡宾阳离子[M-X]⁺(M=Au,Ag,Cu;X=C,CH₂)与甲烷反应机制研究

孙小丽¹, 孟令敏², 金明星³, 李吉来¹

1. 吉林大学理论化学研究所, 长春 130023;
2. 长春迪瑞医疗科技股份有限公司, 长春 130103;
3. 吉林大学原子与分子物理研究所, 长春 130012

收稿日期:2017-01-17 修回日期:2017-07-10 出版日期:2017-08-10 发布日期:2017-07-10
通讯作者: 李吉来,男,博士,教授,博士生导师,主要从事重要化学过程微观机理研究.E-mail:jilai@jlu.edu.cn E-mail:jilai@jlu.edu.cn
基金资助:
国家自然科学基金（批准号：21473070）和中国博士后科学基金（批准号：2016M591476）资助.

Mechanism Research of Reactions of Metal Carbides and Carbenes Cation[M-X] ⁺(M=Au, Ag, Cu; X=C, CH₂) with Methane

SUN Xiaoli¹, MENG Lingmin², JIN Mingxing³, LI Jilai¹

1. Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China;
2. Dirui Industrial Co., Ltd, Changchun 130103, China;
3. Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012, China

Received:2017-01-17 Revised:2017-07-10 Online:2017-08-10 Published:2017-07-10
Supported by:
Supported by the National Natural Science Foundation of China(No.21473070) and the Project of China Postdoctoral Science Foundation(No.2016M591476).

摘要/Abstract

摘要：

在CCSD（T）-REL//B2GP-PLYP水平下构建[Au（CH₂）]⁺与甲烷反应的可靠反应势能面，分析了C-H键活化过程中的几何结构变化情况；对反应IRC路径上关键点进行自然键轨道（NBO）电荷和分子轨道分析，从理论上推定该氢转移过程属于氢负离子（H^-）转移.对[M-X]⁺（M=Au，Ag，Cu；X=C，CH₂）与甲烷反应进行对比，分析了甲烷作为氢供体反应过程的内在影响因素.M-X键能和反应活性中心C上直接参与反应的低能轨道对反应活性均起重要作用，两者协同调控微观反应机制.

关键词: C-H键活化, 卡宾阳离子, 质子转移, 氢原子转移, 氢负离子转移

Abstract:

In this article, the reaction mechanism of the cation[Au(CH₂)] ⁺ and methane was investigated at the CCSD(T)-REL//B2GP-PLYP level of theory initially. A detailed analysis of geometric structure changes during the C-H bond activation was given. As a major result, based on natural bond orbital(NBO) charge and molecular orbital analysis, a hydride transfer mechanistic scenario from methane to[Au(CH₂)] ⁺ was identified unambiguously. Methane activation has been identified among its reaction with[M-X] ⁺(M=Au, Ag, Cu; X=C, CH₂). Analysis for the inherent factors during the reaction of methane as a hydrogen donor is given. The M-X bond energy and the low-lying vacant orbital directly involved in the reaction of the active center C play an important role on the reaction activity, and both mediated microscopic mechanism. This study may provide important guidance for the rational design of catalysts.

Key words: C-H Bond activation, Carbene cation, Proton transfer, Hydrogen atom transfer, Hydride transfer

中图分类号:

O641

TrendMD:

孙小丽, 孟令敏, 金明星, 李吉来. 金属碳,卡宾阳离子[M-X]⁺(M=Au,Ag,Cu;X=C,CH₂)与甲烷反应机制研究. 高等学校化学学报, 2017, 38(8): 1406.

SUN Xiaoli, MENG Lingmin, JIN Mingxing, LI Jilai. Mechanism Research of Reactions of Metal Carbides and Carbenes Cation[M-X] ⁺(M=Au, Ag, Cu; X=C, CH₂) with Methane. Chem. J. Chinese Universities, 2017, 38(8): 1406.

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金属碳,卡宾阳离子[M-X]⁺(M=Au,Ag,Cu;X=C,CH₂)与甲烷反应机制研究

Mechanism Research of Reactions of Metal Carbides and Carbenes Cation[M-X] ⁺(M=Au, Ag, Cu; X=C, CH₂) with Methane

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