Knowledge Management System of Northwest Institute of Plateau Biology, CAS
| Theoretical investigation on the regioselectivity of Ni(COD)(2)-catalyzed [2+2+2] cycloaddition of unsymmetric diynes and CO2 | |
| Zhao, Yi1,3; Liu, Yuxia2; Bi, Siwei2; Liu, Yongjun1 | |
| 2014-05-15 | |
| 发表期刊 | JOURNAL OF ORGANOMETALLIC CHEMISTRY
 |
| ISSN | 0022-328X |
| 卷号 | 758页码:45-54 |
| 文章类型 | Article |
| 摘要 | Reaction mechanisms of the Ni(COD)(2)-catalyzed [2 + 2 + 2] cycloaddition of unsymmetric diynes and CO2 have been theoretically studied by using the density functional theory calculations. Three major steps are included, oxidative coupling of CO2 with Et-substituted C=C bond, the second C=C bond insertion and reductive elimination of the product from the Ni center, in which the C=C bond insertion was found to be rate-determinant. The steric arrangement of the N,P-bidentate ligand was demonstrated to be influential on reaction barriers. Based on the mechanistic study, the regioselectivity of the catalytic reaction was elucidated. In addition, we also explained why the mechanisms involving oxidative coupling of both the C=C bonds are unavailable. (C) 2014 Elsevier B.V. All rights reserved.; Reaction mechanisms of the Ni(COD)(2)-catalyzed [2 + 2 + 2] cycloaddition of unsymmetric diynes and CO2 have been theoretically studied by using the density functional theory calculations. Three major steps are included, oxidative coupling of CO2 with Et-substituted C=C bond, the second C=C bond insertion and reductive elimination of the product from the Ni center, in which the C=C bond insertion was found to be rate-determinant. The steric arrangement of the N,P-bidentate ligand was demonstrated to be influential on reaction barriers. Based on the mechanistic study, the regioselectivity of the catalytic reaction was elucidated. In addition, we also explained why the mechanisms involving oxidative coupling of both the C=C bonds are unavailable. (C) 2014 Elsevier B.V. All rights reserved. |
| 关键词 | Cycloaddition Diyne Pyrone Carbon Dioxide Dft |
| WOS标题词 | Science & Technology ; Physical Sciences |
| 关键词[WOS] | BICYCLIC ALPHA-PYRONES ; CARBON-DIOXIDE ; NICKEL(0)-CATALYZED CYCLOADDITION ; CATALYZED CARBOXYLATION ; ALKENYLBORONIC ESTERS ; COPPER(I) COMPLEXES ; METAL-COMPLEXES ; DENSITY ; ENERGIES ; ALKYNES |
| 收录类别 | SCI |
| 语种 | 英语 |
| WOS研究方向 | Chemistry |
| WOS类目 | Chemistry, Inorganic & Nuclear ; Chemistry, Organic |
| WOS记录号 | WOS:000333247900007 |
| 引用统计 | |
| 文献类型 | 期刊论文 |
| 条目标识符 | http://210.75.249.4/handle/363003/4230 |
| 专题 | 中国科学院西北高原生物研究所 |
| 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 investigation on the regioselectivity of Ni(COD)(2)-catalyzed [2+2+2] cycloaddition of unsymmetric diynes and CO2[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY,2014,758:45-54. |
| APA | Zhao, Yi,Liu, Yuxia,Bi, Siwei,&Liu, Yongjun.(2014).Theoretical investigation on the regioselectivity of Ni(COD)(2)-catalyzed [2+2+2] cycloaddition of unsymmetric diynes and CO2.JOURNAL OF ORGANOMETALLIC CHEMISTRY,758,45-54. |
| MLA | Zhao, Yi,et al."Theoretical investigation on the regioselectivity of Ni(COD)(2)-catalyzed [2+2+2] cycloaddition of unsymmetric diynes and CO2".JOURNAL OF ORGANOMETALLIC CHEMISTRY 758(2014):45-54. |
| 条目包含的文件 | 下载所有文件 | |||||
| 文件名称/大小 | 文献类型 | 版本类型 | 开放类型 | 使用许可 | ||
| Theoretical investig（3229KB） | 开放获取 | CC BY-NC-SA | 浏览 下载 | |||
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