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, Yi1,3; Liu, Yuxia2; Bi, Siwei2; Liu, Yongjun1; 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
 |
| ISSN | 0022-328X |
| 卷号 | 745页码:166-172 |
| 文章类型 | Article |
| 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. |
| 关键词 | Hydrocarboxylation Hydrosilylation Sigma Bond Metathesis Insertion Carbon Dioxide Dft |
| WOS标题词 | Science & Technology ; Physical Sciences |
| DOI | 10.1016/j.jorganchem.2013.07.065 |
| 关键词[WOS] | ALKENYLBORONIC ESTERS ; METAL-COMPLEXES ; CARBOXYLATION ; CO2 ; DENSITY ; PALLADIUM ; TRANSMETALATION ; ENERGIES ; MODEL ; DFT |
| 收录类别 | SCI |
| 语种 | 英语 |
| 项目资助者 | National Natural Science Foundation of China(21173126 ; Sci-Tech Research Project of Shandong Colleges and Universities(J10LB10) ; 21173129) |
| WOS研究方向 | Chemistry |
| WOS类目 | Chemistry, Inorganic & Nuclear ; Chemistry, Organic |
| WOS记录号 | WOS:000326112700024 |
| 引用统计 | |
| 文献类型 | 期刊论文 |
| 条目标识符 | http://210.75.249.4/handle/363003/3898 |
| 专题 | 中国科学院西北高原生物研究所 |
| 通讯作者 | Bi, SW (reprint author), Qufu Normal Univ, Sch Chem & Chem Engn, Qufu 273165, Peoples R China. |
| 作者单位 | 1.Chinese Acad Sci, Northwest Inst Plateau Biol, Xining 810001, Qinghai, Peoples R China 2.Qufu Normal Univ, Sch Chem & Chem Engn, Qufu 273165, Peoples R China 3.Shandong Univ Technol, Sch Chem Engn, Zibo 255049, Peoples R China |
| 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,2013,745:166-172. |
| 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,745,166-172. |
| 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 745(2013):166-172. |
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