Theoretical studies of iridium-mediated tautomerization of substituted pyridines

	Theoretical studies of iridium-mediated tautomerization of substituted pyridines
	Su, Yan 1,2; Song, Guoyong ; Han, Keli 1; Li, Xingwei
刊名	journal of organometallic chemistry
	2011-04-15
卷号	696 期号:8 页码:1640-1646
关键词	Tautomerization N-heterocyclic carbenes Density functional calculations
ISSN号	待补充
通讯作者	韩克利 ; 李兴伟
产权排序	1,1
中文摘要	theoretical studies of iridium-mediated tautomerization of substituted pyridines
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.
学科主题	物理化学
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]	n-heterocyclic carbene ; density-functional thermochemistry ; h bond activation ; cross-coupling reactions ; c-h ; 2-substituted pyridines ; agostic interactions ; complexes ; mechanism ; ruthenium
收录类别	SCI
语种	英语
WOS记录号	WOS:000289072300020
公开日期	2012-07-09
内容类型	期刊论文
源URL	[http://159.226.238.44/handle/321008/115612]
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	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
推荐引用方式 GB/T 7714	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.
APA	Su, Yan,Song, Guoyong,Han, Keli,&Li, Xingwei.(2011).Theoretical studies of iridium-mediated tautomerization of substituted pyridines.journal of organometallic chemistry,696(8),1640-1646.
MLA	Su, Yan,et al."Theoretical studies of iridium-mediated tautomerization of substituted pyridines".journal of organometallic chemistry 696.8(2011):1640-1646.