金(I)配合物催化乙烯加氢的反应机理

引用本文: 仇毅翔, 万明达, 陈先阳, 王曙光. 金(I)配合物催化乙烯加氢的反应机理[J]. 物理化学学报, 2013, 29(02): 279-286. doi: 10.3866/PKU.WHXB201212061 shu

Citation: QIU Yi-Xiang, WAN Ming-Da, CHEN Xian-Yang, WANG Shu-Guang. Reaction Mechanisms of Ethylene Hydrogenation Catalyzed by ld(I) Complexes[J]. Acta Physico-Chimica Sinica, 2013, 29(02): 279-286. doi: 10.3866/PKU.WHXB201212061 shu

金(I)配合物催化乙烯加氢的反应机理

基金项目:
国家自然科学基金(20973109) (20973109)

国家大学生创新性实验计划(S110ITP5009) (S110ITP5009)

上海交通大学大学生创新实践计划(IPP6123, IPP6128)资助项目 (IPP6123, IPP6128)

摘要:

采用密度泛函理论B3LYP方法, 对两类金(I)配合物AuX (X=F, Cl, Br, I)和AuPR₃⁺(R=F, Cl, Br, I, H, Me,Ph)催化C₂H₄加氢反应的机理进行了理论研究. 计算显示Au(I)配合物对C₂H₄氢化具有较好的催化效果, 其作用下的加氢反应存在“活化H―H键后再与C₂H₄反应”和“活化C＝C键后再与H₂反应”两种途径, 前者的活化能较后者低90-120 kJ·mol^-1, 因而具有明显的能量优势. 研究表明AuPR₃⁺ 的催化能力明显强于AuX. 此外, X/PR3基团供、吸电子能力的变化对配合物的催化能力也具有较为显著的影响. 电子结构分析显示Au(I)配合物在C₂H₄ 加氢反应中不仅能够削弱H―H、C＝C 键的强度, 还使H₂ σ_H―H^*、C₂H₄ π_C＝C^* 轨道能级下降, 从而缩小了π_C＝C-σ_H―H^*或σ_H―H-π_C＝C^*轨道间的能级差, 促进了C₂H₄-H₂反应中的电子离域, 从而降低禁阻反应发生的难度.σ_H―H^*、π_C＝C^*轨道能级改变量与加氢反应活化能E_a的降低值之间存在较好的一致性关系, 因此使上述轨道能级下降幅度越大的Au(I)配合物可以获得较好的催化效果.

关键词:

English

Reaction Mechanisms of Ethylene Hydrogenation Catalyzed by ld(I) Complexes

1.
School of Chemistry and Chemical Technology, Shanghai Jiaotong University, Shanghai 200240
Received Date: 27 June 2012
Available Online: 14 January 2013
Fund Project:
国家自然科学基金(20973109)

国家大学生创新性实验计划(S110ITP5009)

上海交通大学大学生创新实践计划(IPP6123, IPP6128)资助项目

Abstract:

The reaction mechanisms of ethylene hydrogenation catalyzed by Au(I) complexes AuX (X=F, Cl, Br, I) and AuPR₃⁺ (R = F, Cl, Br, I, H, Me, Ph) were investigated using density functional theory at the B3LYP level. The calculated results indicated that Au(I) complexes were effective catalysts in the hydrogenation of ethylene. AuPR₃⁺ showed higher catalytic activity than AuX and the effect of changing the electron donating or withdrawing ability of the ligand on catalytic activity was large. Natural bond orbital analysis indicated that the interactions between the Au(I) complex and H₂/C₂H₄ not only weakened the H― H/C＝C bond strength, but also decreased the energy of the σ_H―H^*、π_C＝C^* orbital level. As a result, the energy differences of π_C＝C-σ_H―H^*/σ_H―H-π_C＝C^* decreased, and ethylene hydrogenation was facilitated. A linear correlation was observed between the activation energies and π_C＝C-σ_H―H^*/σ_H―H-π_C＝C^*. The more an Au(I) complex affected the σ_H―H^*/π_C＝C^* orbital levels, the higher its catalytic activity.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

金(I)配合物催化乙烯加氢的反应机理

English

Reaction Mechanisms of Ethylene Hydrogenation Catalyzed by ld(I) Complexes

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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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

金(I)配合物催化乙烯加氢的反应机理

English

Reaction Mechanisms of Ethylene Hydrogenation Catalyzed by ld(I) Complexes

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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