Knowledge Management System of Northwest Institute of Plateau Biology, CAS
Theoretical study on copper-catalyzed reaction of hydrosilane, alkyne and carbon dioxide: A hydrocarboxylation or a hydrosilylation process ? | |
Zhao, Yi ; Liu, Yuxia ; Bi, Siwei ; Liu, Yongjun ; Bi, SW (reprint author), Qufu Normal Univ, Sch Chem & Chem Engn, Qufu 273165, Peoples R China. | |
2013-11-15 | |
发表期刊 | JOURNAL OF ORGANOMETALLIC CHEMISTRY ; Zhao, Y; Liu, YX; Bi, SW; Liu, YJ.Theoretical study on copper-catalyzed reaction of hydrosilane, alkyne and carbon dioxide: A hydrocarboxylation or a hydrosilylation process ?,JOURNAL OF ORGANOMETALLIC CHEMISTRY,2013,745():166-172 |
摘要 | The hydrocarboxylation and hydrosilylation processes proposed in the copper-catalyzed reaction among carbon dioxide, diphenylacetylene and HSi(OEt)(3) were comparatively studied with the aid of density functional theory calculations. Our study is to explore why the reaction preferred a hydrocarboxylation rather than a hydrosilylation process. It was found that the sigma bond metathesis between Cu-C and H-Si involved in the hydrosilylation process had a significantly high reaction barrier in the presence of CO2 (47.4 kcal/mol). Instead, CO2 insertion and the subsequent s bond metathesis between Cu-O and H-Si involved in the hydrocarboxylation process were confirmed kinetically feasible, consistent with the experimental facts. (C) 2013 Elsevier B. V. All rights reserved.; The hydrocarboxylation and hydrosilylation processes proposed in the copper-catalyzed reaction among carbon dioxide, diphenylacetylene and HSi(OEt)(3) were comparatively studied with the aid of density functional theory calculations. Our study is to explore why the reaction preferred a hydrocarboxylation rather than a hydrosilylation process. It was found that the sigma bond metathesis between Cu-C and H-Si involved in the hydrosilylation process had a significantly high reaction barrier in the presence of CO2 (47.4 kcal/mol). Instead, CO2 insertion and the subsequent s bond metathesis between Cu-O and H-Si involved in the hydrocarboxylation process were confirmed kinetically feasible, consistent with the experimental facts. (C) 2013 Elsevier B. V. All rights reserved. |
文献类型 | 期刊论文 |
条目标识符 | http://210.75.249.4/handle/363003/16671 |
专题 | 中国科学院西北高原生物研究所 |
推荐引用方式 GB/T 7714 | Zhao, Yi,Liu, Yuxia,Bi, Siwei,et al. Theoretical study on copper-catalyzed reaction of hydrosilane, alkyne and carbon dioxide: A hydrocarboxylation or a hydrosilylation process ?[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, Zhao, Y; Liu, YX; Bi, SW; Liu, YJ.Theoretical study on copper-catalyzed reaction of hydrosilane, alkyne and carbon dioxide: A hydrocarboxylation or a hydrosilylation process ?,JOURNAL OF ORGANOMETALLIC CHEMISTRY,2013,745():166-172,2013. |
APA | Zhao, Yi,Liu, Yuxia,Bi, Siwei,Liu, Yongjun,&Bi, SW .(2013).Theoretical study on copper-catalyzed reaction of hydrosilane, alkyne and carbon dioxide: A hydrocarboxylation or a hydrosilylation process ?.JOURNAL OF ORGANOMETALLIC CHEMISTRY. |
MLA | Zhao, Yi,et al."Theoretical study on copper-catalyzed reaction of hydrosilane, alkyne and carbon dioxide: A hydrocarboxylation or a hydrosilylation process ?".JOURNAL OF ORGANOMETALLIC CHEMISTRY (2013). |
条目包含的文件 | 条目无相关文件。 |
除非特别说明,本系统中所有内容都受版权保护,并保留所有权利。
修改评论