DFT Studies on the Methane Elimination Reaction of a Trinuclear Rare-Earth Polymethyl Complex: (sigma-Bond Metathesis Assisted by Cooperation of Multimetal Sites
文献类型：期刊论文
| 作者 | Luo, Gen1; Luo, Yi1; Zhang, Wenxiong2,3; Qu, Jingping1; Hou, Zhaomin1,4 |
| 刊名 | ORGANOMETALLICS
 |
| 出版日期 | 2014-03-10 |
| 卷号 | 33期号:5页码:1126-1134 |
| ISSN号 | 0276-7333 |
| DOI | 10.1021/om400920x |
| 英文摘要 | DFT studies have been performed for the process of methane elimination via an intramolecular C-H bond activation of the polymethyl trinuclear rare-earth-metal complex [(eta(5)-C5Me4SiMe3)Tm(mu(2)-CH3)(2)](3). It has been found that intermetallic cooperation plays an important role in achieving such an intramolecular C-H bond activation process, and the cooperation of trimetallic centers makes the C-H bond activation kinetically easier in comparison with that of bimetallic centers. The methane elimination reaction occurs through rearrangement of Tm-CH3 connections and subsequent C-H bond activation. The C-H bond activation is the rate-determining step of the whole process, and the corresponding transition state is characterized by a sigma-bond metathesis assisted by cooperation of multimetal sites. Such a C-H bond activation step was accomplished by a change in the coordination manner (from mu(2) to mu(3) fashion) of a methyl group and a subsequent hydrogen transfer, and the two events are asynchronous concerted processes. The computational results also suggest that the reactivity of the CH bond of the metal-connected CH3 group follows the order mu(3)-C(H-2)-H > mu(2)-C(H-2)H > mu(1)-C(H-2)-H. This is unlike the case of a metal-CH3 bond, where the terminal methyl (monometal-connected mu(1)-CH3) is generally more reactive than multimetal-connected methyls. In addition, the effect of 4f electrons of such trinuclear organolanthanide compounds on the geometry and energy profile studied here is also discussed. |
| 语种 | 英语 |
| WOS记录号 | WOS:000332756800007 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/50741]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Luo, Yi |
| 作者单位 | 1.Dalian Univ Technol, State Key Lab Fine Chem, Sch Pharmaceut Sci & Technol, Dalian 116024, Peoples R China 2.Peking Univ, BNLMS, Coll Chem, Beijing 100871, Peoples R China 3.Peking Univ, Key Lab Bioorgan Chem & Mol Engn, Coll Chem, Minist Educ, Beijing 100871, Peoples R China 4.RIKEN, Organometall Chem Lab, Wako, Saitama 3510198, Japan |
| 推荐引用方式 GB/T 7714 | Luo, Gen,Luo, Yi,Zhang, Wenxiong,et al. DFT Studies on the Methane Elimination Reaction of a Trinuclear Rare-Earth Polymethyl Complex: (sigma-Bond Metathesis Assisted by Cooperation of Multimetal Sites[J]. ORGANOMETALLICS,2014,33(5):1126-1134. |
| APA | Luo, Gen,Luo, Yi,Zhang, Wenxiong,Qu, Jingping,&Hou, Zhaomin.(2014).DFT Studies on the Methane Elimination Reaction of a Trinuclear Rare-Earth Polymethyl Complex: (sigma-Bond Metathesis Assisted by Cooperation of Multimetal Sites.ORGANOMETALLICS,33(5),1126-1134. |
| MLA | Luo, Gen,et al."DFT Studies on the Methane Elimination Reaction of a Trinuclear Rare-Earth Polymethyl Complex: (sigma-Bond Metathesis Assisted by Cooperation of Multimetal Sites".ORGANOMETALLICS 33.5(2014):1126-1134. |
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来源：化学研究所
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