Theoretical Mechanistic Study of Nickel(0)Lewis Acid Catalyzed Polyfluoroarylcyanation of Alkynes  Origin of Selectivity for C-CN Bond Activation

doi:10.1021/acs.organomet.8b00338

CIOMP OpenIR

	Theoretical Mechanistic Study of Nickel(0)Lewis Acid Catalyzed Polyfluoroarylcyanation of Alkynes Origin of Selectivity for C-CN Bond Activation
	Ren, H.; Du, G. F.; Zhu, B.; Yang, G. C.; Yao, L. S.; Guan, W.; Su, Z. M.
	2018
发表期刊	Organometallics
ISSN	0276-7333
卷号	37 期号:15 页码:2594-2601
摘要	The cooperative mechanism of Ni(0)/Lewis acid catalyzed carbocyanation of alkyne with 2,3,5,6-tetrafluorobenzonitrile was investigated using the DFT method. Our calculations indicate that the most feasible catalytic cycle consists of the oxidative addition of a C-CN bond to the Ni(0) center, alkyne insertion into the C(aryl)-Ni(II) bond, and reductive elimination. Notably, the Lewis acid (LA) interacting with the cyano nitrogen atom of the substrate can have a significant effect on activating the C-CN bond while suppressing C-H and C-F bond activations. The origin of lower C-CN activation barrier in the presence of LA can be attributed to the remarkably enhanced charge transfer (CT) amount from the Ni-cat 3d orbital to C-CN sigma+pi antibonding molecular orbital and the little decrease of interaction energy between Ni-catalyst and substrate. In the C-F and C-H bond activations in the presence of LA, on the contrary, the significant decrease of interaction energy between Ni-catalyst and substrate and almost no change of charge transfer amounts are the origin of the larger bond activation barrier. Thus, LA is essential to make the C-CN bond weaker than other bonds, which agrees well with the experimental observation. Electronic processes as well as interaction energy analyses are discussed in detail.
关键词	carbon-carbon bonds oxidative addition organic-synthesis h activation sigma-bond cooperative catalysis transition-elements assisted cleavage zerovalent nickel metal-complexes Chemistry
DOI	10.1021/acs.organomet.8b00338
收录类别	SCI ; EI
引用统计
文献类型	期刊论文
条目标识符	http://ir.ciomp.ac.cn/handle/181722/61187
专题	中国科学院长春光学精密机械与物理研究所
推荐引用方式 GB/T 7714	Ren, H.,Du, G. F.,Zhu, B.,et al. Theoretical Mechanistic Study of Nickel(0)Lewis Acid Catalyzed Polyfluoroarylcyanation of Alkynes Origin of Selectivity for C-CN Bond Activation[J]. Organometallics,2018,37(15):2594-2601.
APA	Ren, H..,Du, G. F..,Zhu, B..,Yang, G. C..,Yao, L. S..,...&Su, Z. M..(2018).Theoretical Mechanistic Study of Nickel(0)Lewis Acid Catalyzed Polyfluoroarylcyanation of Alkynes Origin of Selectivity for C-CN Bond Activation.Organometallics,37(15),2594-2601.
MLA	Ren, H.,et al."Theoretical Mechanistic Study of Nickel(0)Lewis Acid Catalyzed Polyfluoroarylcyanation of Alkynes Origin of Selectivity for C-CN Bond Activation".Organometallics 37.15(2018):2594-2601.

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 Mechanis（1912KB）	期刊论文	出版稿	开放获取	CC BY-NC-SA	浏览下载