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理论方法研究碳双卡宾催化活化二氧化碳机理

发表时间:2016-10-15  浏览量:1780  下载量:559
全部作者: 许哲远,张琪,蒋原野,傅尧
作者单位: 中国科学技术大学化学与材料科学学院
摘 要: CO2还原是CO2化学转化中的一个关键步骤。除过渡金属、碳卡宾、路易斯酸/碱之外,碳双卡宾最近也被发现具有催化CO2还原的能力。采用密度泛函理论(density functional theory,DFT)方法对碳双卡宾活化CO2的反应机理进行研究。计算结果显示,碳双卡宾催化剂活化CO2历经碳双卡宾对9-硼二环[3.3.1]壬烷(9-borabicyclo [3.3.1] nonane,9-BBN)的亲核进攻、氢原子迁移和C—B键断裂。另一方面,碳双卡宾催化剂和9-BBN形成的加成产物通过CO2插入和氢原子迁移活化CO2. 相比之下,后一种路径中的氢原子迁移在动力学上更加困难,导致该加合物反应活性低于碳双卡宾催化剂。
关 键 词: 有机化学;二氧化碳;密度泛函理论;还原
Title: Theoretical study on catalytic activation of carbon dioxide by carbodicarbenes
Author: XU Zheyuan, ZHANG Qi, JIANG Yuanye, FU Yao
Organization: School of Chemistry and Materials Science, University of Science and Technology of China
Abstract: Reduction of CO2 is a critical process in chemical transformations of CO2. In addition to transition metals, carbenes and Lewis acids/bases, carbodicarbenes have recently been demonstrated to be capable of activating CO2. In this paper, density functional theory (DFT) methods were employed to investigate the mechanism of CO2 activation by carbodicarbenes. Calculation results indicate that the activation of CO2 by carbodicarbenes proceeds via nucleophilic attack of carbodicarbene to 9-borabicyclo [3.3.1] nonane (9-BBN), hydrogen atom transfer and C—B bond cleavage. On the other hand, the adduct of carbodicarbenes and 9-BBN activates CO2 through insertion of CO2 and hydrogen atom transfer. By comparison, the hydrogen atom transfer in the later case is more kinetically difficult, making the catalytic activity of the adduct lower than that of carbodicarbenes.
Key words: organic chemistry; carbon dioxide; density functional theory; reduction
发表期数: 2016年10月第19期
引用格式: 许哲远,张琪,蒋原野,等. 理论方法研究碳双卡宾催化活化二氧化碳机理[J]. 中国科技论文在线精品论文,2016,9(19):2023-2029.
 
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