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题名: Theoretical studies on the intra- and intermolecular C-H activation by T-shaped pincer complexes
作者: Feng, Yifan1, 2;  Wang, Changsheng1;  Fan, Hongjun2
关键词: C-H activation ;  Pincer compound ;  PNP ;  Ligand modification ;  Intramolecular ;  Intermolecular
刊名: JOURNAL OF ORGANOMETALLIC CHEMISTRY
发表日期: 2011-12-15
DOI: 10.1016/j.jorganchem.2011.06.039
卷: 696, 期:25, 页:4064-4069
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Inorganic & Nuclear ;  Chemistry, Organic
研究领域[WOS]: Chemistry
英文摘要: Three coordinated, T-shaped (PNP)M-I (M Co, Ru, Rh, Os and Ir) and [(PCP) Pt0]-, as well as their reactivities for intra- and intermolecular C-H activation have been studied by DFT methods. The experimental observed reactivities were well reproduced. The calculation also generated structural and energetic information which the experimental values were not yet available. We found that the intramolecular C-H activation is in general possible for the low spin (PNP)M-I. Intermolecular C-H activation is not preferred either thermodynamically or kinetically, but could be in competition if the intramolecular activation is reversible. Using model compounds, we found that the intramolecular C-H activation reactivity is not sensitive to steric effects of the bulky ligands. However, the strain of the four-membered ring in the product significantly reduces the reactivity, and the driving force increases by 4.51 -12.95 kcal/mol if the strain was largely removed by changing from a four-membered ring to a five-membered ring. The C-H activation step is quite difficult for metals with a d(10) configuration. Part of the reason is that one phosphine ligand dissociates during the reaction because the product has a d(8) configuration and prefers a square planar structure. (C) 2011 Elsevier B.V. All rights reserved.
关键词[WOS]: EFFECTIVE CORE POTENTIALS ;  BOND ACTIVATION ;  MOLECULAR CALCULATIONS ;  METAL-COMPLEXES ;  AB-INITIO ;  TRANSFER DEHYDROGENATION ;  OXIDATIVE-ADDITION ;  CHEMISTRY ;  HYDROGEN ;  DENSITY
语种: 英语
WOS记录号: WOS:000297152600023
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/142667
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.Liaoning Normal Univ, Coll Chem & Chem Engn, Dalian 116029, Peoples R China
2.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China

Recommended Citation:
Feng, Yifan,Wang, Changsheng,Fan, Hongjun. Theoretical studies on the intra- and intermolecular C-H activation by T-shaped pincer complexes[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY,2011,696(25):4064-4069.
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