Theoretical studies on the intra- and intermolecular C-H activation by T-shaped pincer complexes
文献类型：期刊论文
| 作者 | Feng, Yifan1,2; Wang, Changsheng1; Fan, Hongjun2 |
| 刊名 | journal of organometallic chemistry
 |
| 出版日期 | 2011-12-15 |
| 卷号 | 696期号:25页码:4064-4069 |
| 关键词 | C-H activation Pincer compound PNP Ligand modification Intramolecular Intermolecular |
| 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. |
| 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] | effective core potentials ; bond activation ; molecular calculations ; metal-complexes ; ab-initio ; transfer dehydrogenation ; oxidative-addition ; chemistry ; hydrogen ; density |
| 收录类别 | SCI |
| 语种 | 英语 |
| WOS记录号 | WOS:000297152600023 |
| 公开日期 | 2015-11-17 |
| 源URL | [http://159.226.238.44/handle/321008/142667]  |
| 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.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 |
| 推荐引用方式 GB/T 7714 | 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. |
| APA | Feng, Yifan,Wang, Changsheng,&Fan, Hongjun.(2011).Theoretical studies on the intra- and intermolecular C-H activation by T-shaped pincer complexes.journal of organometallic chemistry,696(25),4064-4069. |
| MLA | Feng, Yifan,et al."Theoretical studies on the intra- and intermolecular C-H activation by T-shaped pincer complexes".journal of organometallic chemistry 696.25(2011):4064-4069. |
入库方式： OAI收割
来源：大连化学物理研究所
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