Theoretical investigation on the regioselectivity of Ni(COD)(2)-catalyzed [2+2+2] cycloaddition of unsymmetric diynes and CO2

NWIPB OpenIR

	Theoretical investigation on the regioselectivity of Ni(COD)(2)-catalyzed [2+2+2] cycloaddition of unsymmetric diynes and CO2
	Zhao, Yi ; Liu, Yuxia ; Bi, Siwei ; Liu, Yongjun
	2014-05-15
发表期刊	JOURNAL OF ORGANOMETALLIC CHEMISTRY ; Zhao, Y; Liu, YX; Bi, SW; Liu, YJ.Theoretical investigation on the regioselectivity of Ni(COD)(2)-catalyzed [2+2+2] cycloaddition of unsymmetric diynes and CO2,JOURNAL OF ORGANOMETALLIC CHEMISTRY,2014,758():45
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.
文献类型	期刊论文
条目标识符	http://210.75.249.4/handle/363003/22094
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 investigation on the regioselectivity of Ni(COD)(2)-catalyzed [2+2+2] cycloaddition of unsymmetric diynes and CO2[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, Zhao, Y; Liu, YX; Bi, SW; Liu, YJ.Theoretical investigation on the regioselectivity of Ni(COD)(2)-catalyzed [2+2+2] cycloaddition of unsymmetric diynes and CO2,JOURNAL OF ORGANOMETALLIC CHEMISTRY,2014,758():45,2014.
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.
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 (2014).