DFT investigation on mechanism of dirhodium tetracarboxylate-catalyzed O-H insertion of diazo compounds with H2O

	DFT investigation on mechanism of dirhodium tetracarboxylate-catalyzed O-H insertion of diazo compounds with H2O
	Liu, Zhenfeng; Liu, Jianyong
刊名	central european journal of chemistry
	2010-02-01
卷号	8 期号:1 页码:223-228
关键词	DFT calculations Diazo compounds Dirhodium tetracarboxylate-catalyzed O-H insertion reaction
英文摘要	the mechanism of the dirhodium tetracarboxylate-catalyzed o-h insertion reaction of diazomethane and methyl diazoacetate with h2o has been studied in detail using dft calculations. the rhodium catalyst and a diazo compound couple to form a rhodiumcarbene complex. of two reaction pathways of the rh(ii)-carbene complex with h2o, the stepwise pathway is more preferable than the concerted one. formation of a rh(ii) complex-associated oxonium ylide is an exothermal process, and direct decomposition of the ylide gives a very high barrier. the high barriers for the 1,2-h shift of rh(ii) complex-associated oxonium ylides make the ylides become stable intermediates in both reactions, especially for the reactions in solution. difficulty in formation of a free oxonium ylide supports experimental results, indicating that the rh(ii) complex-catalyzed nucleophilic addition of a diazo compound proceeds via a rh(ii) complex-associated oxonium ylide rather than via a free oxonium ylide.
WOS标题词	science & technology ; physical sciences
类目[WOS]	chemistry, multidisciplinary
研究领域[WOS]	chemistry
关键词[WOS]	carbonyl ylide formation ; effective core potentials ; free-energy correlation ; ab-initio ; molecular calculations ; asymmetric-synthesis ; 3-component reaction ; stepwise mechanism ; chemical-reactions ; carbenoids
收录类别	SCI
语种	英语
WOS记录号	WOS:000276548100029
公开日期	2015-11-17
内容类型	期刊论文
源URL	[http://159.226.238.44/handle/321008/142164]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
作者单位	Chinese Acad Sci, Dalian Inst Chem Phys, Dalian 116023, Peoples R China
推荐引用方式 GB/T 7714	Liu, Zhenfeng,Liu, Jianyong. DFT investigation on mechanism of dirhodium tetracarboxylate-catalyzed O-H insertion of diazo compounds with H2O[J]. central european journal of chemistry,2010,8(1):223-228.
APA	Liu, Zhenfeng,&Liu, Jianyong.(2010).DFT investigation on mechanism of dirhodium tetracarboxylate-catalyzed O-H insertion of diazo compounds with H2O.central european journal of chemistry,8(1),223-228.
MLA	Liu, Zhenfeng,et al."DFT investigation on mechanism of dirhodium tetracarboxylate-catalyzed O-H insertion of diazo compounds with H2O".central european journal of chemistry 8.1(2010):223-228.