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题名: DFT investigation on mechanism of dirhodium tetracarboxylate-catalyzed O-H insertion of diazo compounds with H2O
作者: Liu, Zhenfeng1;  Liu, Jianyong1
关键词: DFT calculations ;  Diazo compounds ;  Dirhodium tetracarboxylate-catalyzed O-H insertion reaction
刊名: CENTRAL EUROPEAN JOURNAL OF CHEMISTRY
发表日期: 2010-02-01
DOI: 10.2478/s11532-009-0118-8
卷: 8, 期:1, 页:223-228
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Multidisciplinary
研究领域[WOS]: Chemistry
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.
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
语种: 英语
WOS记录号: WOS:000276548100029
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/142164
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, Dalian Inst Chem Phys, Dalian 116023, Peoples R China

Recommended Citation:
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.
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