DOI: 10.1016/j.jcou.2017.05.016
Scopus记录号: 2-s2.0-85020009106
论文题名: Theoretical investigations on the methylation of N-H bond using CO2 and hydrosilane catalyzed by ZincII complexes: Mechanism and ligand effect
作者: Li W. ; Kim C.K.
刊名: Journal of CO2 Utilization
ISSN: 22129820
出版年: 2017
卷: 20 起始页码: 178
结束页码: 189
语种: 英语
英文关键词: Carbon dioxide reduction
; Catalysis by Zn complexes
; Methylation of N-methylaniline
; SN2@Si-Acceptor mechanism
Scopus关键词: Alkylation
; Carbon
; Catalysis
; Chemical activation
; Chemical bonds
; Density functional theory
; Ligands
; Methylation
; Organic compounds
; Pollution control
; Reduction
; Silicon
; Zinc
; Carbon dioxide reduction
; Carbonyl oxygen atoms
; Catalytic mechanisms
; N-heterocyclic carbene ligands
; N-methylaniline
; Rate-determining step
; Theoretical investigations
; Zn complex
; Carbon dioxide
英文摘要: The detailed catalytic mechanisms of zincII complexes in the methylation of the N-H bond of N-methylaniline with CO2 and hydrosilane (PhSiH3) were studied using density functional theory (DFT) calculations. Among all the examined catalytic reaction pathways, we found that the most favorable pathway is composed of two stages: the formation of the formamide (FA) species and the reduction of the FA species to the target product methylamine (MA). Over the zinc complexes, the FA species formation begins with the reaction of N-methylaniline with CO2, followed by the reduction of CO2 with PhSiH3 to the formoxysilane (FOS) species. The formation of the FOS species prefers to proceed through the "SN2@Si-Acceptor" Si-H bond activation mechanism and is predicted to be the rate-determining step (RDS) for the overall reaction. The ammonium carbamate (AC) zwitterion generated in the reaction of N-methylaniline with CO2 is the nucleophilic species to promote Si-H bond activation, and the zinc complex is demonstrated to be effective in facilitating the C-N bond formation in the reaction of N-methylaniline with CO2 and stabilizing the nucleophilic AC zwitterion. The calculations reveal that the N-heterocyclic carbene (NHC) ligand plays two main roles in the reaction. (i) Preventing the coordination of the FA species to the zinc center and avoiding a decrease in the nucleophilicity of the carbonyl oxygen atom in the FA species, and (ii) lowering the Lewis acidity of the zinc center, which makes the activity of the Si-H bond less decreased. © 2017 Elsevier Ltd. All rights reserved.. Citation statistics:
资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/52691
Appears in Collections: 影响、适应和脆弱性
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Recommended Citation:
Li W.,Kim C.K.. Theoretical investigations on the methylation of N-H bond using CO2 and hydrosilane catalyzed by ZincII complexes: Mechanism and ligand effect[J]. Journal of CO2 Utilization,2017-01-01,20