Dinuclear versus mononuclear pathways in zinc mediated nucleophilic addition: a combined experimental and DFT study | |
Qi, Xiaotian1,2; Li, Yingzi1; Zhang, Guanghui2; Li, Yang1; Lei AW(雷爱文)2; Liu C(刘超)2,3![]() ![]() | |
刊名 | Dalton Transactions
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2015 | |
卷号 | 44期号:24页码:11165-11171 |
ISSN号 | 1477-9226 |
通讯作者 | 雷爱文 ; 刘超 ; Lan, Yu |
英文摘要 | Employing the oxidative coupling of phenylacetylene with benzaldehyde as a model reaction, a density functional theory (DFT) study combined with extended X-ray absorption fine structure (EXAFS) experiment was carried out to reveal the difference between dinuclear and mononuclear zinc mediated nucleophilic addition. Newly reported DFT method M11-L computed results suggest that the mononuclear zinc mediated pathway, in which nucleophilic addition occurs via a four-membered ring transition state, is unfavourable both thermodynamically and kinetically. The dinuclear zinc mechanism, which appropriately explains the experimental observations, involves a six-membered ring transition state for nucleophilic addition. Subsequent in situ EXAFS experiment confirmed the existence of dinuclear zinc active species. Moreover, frontier molecular orbital (FMO) analysis and distortion–interaction energy analysis along the whole reaction pathways have provided interpretations for the advantage of dinuclear zinc mediated nucleophilic addition. Consequently, we believe this dinuclear zinc pathway will open up a general consideration of the dinuclear zinc mechanism for nucleophilic additions. |
学科主题 | 物理化学与绿色催化 |
收录类别 | SCI |
资助信息 | the National Science Foun¬dation of China (Grants 21372266;21372268;51302327;21302148;21390400;21025206);the 973 Program (2012CB725302);the Foundation of 100YOUNG Chong¬qing University (project 0903005203191);the project (no. 106112015CDJZR228806);the Fundamental Research Funds for the Central Universities (Chongqing University) |
语种 | 英语 |
WOS记录号 | WOS:000356056900033 |
公开日期 | 2015-12-24 |
内容类型 | 期刊论文 |
源URL | [http://210.77.64.217/handle/362003/18485] ![]() |
专题 | 兰州化学物理研究所_OSSO国家重点实验室 |
通讯作者 | Liu C(刘超) |
作者单位 | 1.Chongqing Univ, Sch Chem & Chem Engn, Chongqing 400030, Peoples R China 2.Wuhan Univ, Coll Chem & Mol Sci, Wuhan 430072, Hubei, Peoples R China 3.Chinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China |
推荐引用方式 GB/T 7714 | Qi, Xiaotian,Li, Yingzi,Zhang, Guanghui,et al. Dinuclear versus mononuclear pathways in zinc mediated nucleophilic addition: a combined experimental and DFT study[J]. Dalton Transactions,2015,44(24):11165-11171. |
APA | Qi, Xiaotian.,Li, Yingzi.,Zhang, Guanghui.,Li, Yang.,Lei AW.,...&刘超.(2015).Dinuclear versus mononuclear pathways in zinc mediated nucleophilic addition: a combined experimental and DFT study.Dalton Transactions,44(24),11165-11171. |
MLA | Qi, Xiaotian,et al."Dinuclear versus mononuclear pathways in zinc mediated nucleophilic addition: a combined experimental and DFT study".Dalton Transactions 44.24(2015):11165-11171. |
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