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学科主题: 物理化学
题名: Theoretical studies of iridium-mediated tautomerization of substituted pyridines
作者: Su, Yan1, 2;  Song, Guoyong;  Han, Keli1;  Li, Xingwei
通讯作者: 韩克利 ;  李兴伟
关键词: Tautomerization ;  N-heterocyclic carbenes ;  Density functional calculations
刊名: JOURNAL OF ORGANOMETALLIC CHEMISTRY
发表日期: 2011-04-15
DOI: 10.1016/j.jorganchem.2011.01.029
卷: 696, 期:8, 页:1640-1646
收录类别: SCI
文章类型: Article
部门归属: 11;2
项目归属: 1101;02T3
产权排名: 1,1
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Inorganic & Nuclear ;  Chemistry, Organic
摘要: Theoretical studies of iridium-mediated tautomerization of substituted pyridines
研究领域[WOS]: Chemistry
英文摘要: Room temperature reaction of [Ir(COD)(2)]BF4 (COD - 1,5-cyclooctadiene) and amide-tethered or simple 2,3'-bipyridyls gave iridium(I) complexes bearing chelating protic pyridylidenes. This protic pyridylidene tautomer is stabilized by both chelation effect and by hydrogen bonding. The mechanistic details of this tautomerization of N-heterocycles to N-heterocyclic carbenes (NHCs) were investigated using the density functional theory (DFT). DFT studies suggested that cyclometalation of 2,3'-bipyridyls took place to give an iridium(III) hydride, which subsequently undergoes formal 1,3-hydrogen shift from the iridium to the pyridyl nitrogen atom. Two possible mechanisms of this formal 1,3-hydrogen shift process have been examined: the beta-insertion of the hydride into an olefin followed by proton abstraction and the water-assisted proton transfer via a cyclic transition state. The latter mechanism is strongly favored in the presence of a catalytic amount of water, and this mechanism is applicable to the tautomerization of both amide-tethered and amide-free 2,3'-bipyridyls. (C) 2011 Elsevier B. V. All rights reserved.
关键词[WOS]: N-HETEROCYCLIC CARBENE ;  DENSITY-FUNCTIONAL THERMOCHEMISTRY ;  H BOND ACTIVATION ;  CROSS-COUPLING REACTIONS ;  C-H ;  2-SUBSTITUTED PYRIDINES ;  AGOSTIC INTERACTIONS ;  COMPLEXES ;  MECHANISM ;  RUTHENIUM
语种: 英语
WOS记录号: WOS:000289072300020
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/115612
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, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China
2.Chinese Acad Sci, Grad Sch, Beijing 100049, Peoples R China

Recommended Citation:
Su, Yan,Song, Guoyong,Han, Keli,et al. Theoretical studies of iridium-mediated tautomerization of substituted pyridines[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY,2011,696(8):1640-1646.
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