Theoretical study on copper-catalyzed reaction of hydrosilane, alkyne and carbon dioxide: A hydrocarboxylation or a hydrosilylation process ?

	Theoretical study on copper-catalyzed reaction of hydrosilane, alkyne and carbon dioxide: A hydrocarboxylation or a hydrosilylation process ?
	Zhao, Yi 1,3; Liu, Yuxia 2; Bi, Siwei 2; Liu, Yongjun 1
刊名	journal of organometallic chemistry
	2013-11-15
卷号	745 页码:166-172
关键词	Hydrocarboxylation Hydrosilylation sigma bond metathesis Insertion Carbon dioxide DFT
ISSN号	0022-328x
通讯作者	bi, sw (reprint author), qufu normal univ, sch chem & chem engn, qufu 273165, peoples r china.
中文摘要	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.
英文摘要	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.
WOS标题词	science & technology ; physical sciences
类目[WOS]	chemistry, inorganic & nuclear ; chemistry, organic
研究领域[WOS]	chemistry
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
WOS记录号	WOS:000326112700024
公开日期	2014-05-09
内容类型	期刊论文
源URL	[http://ir.nwipb.ac.cn/handle/363003/3898]
专题	西北高原生物研究所_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 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.(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.