Spin-dependent effects in ethylene polymerization with bis(imino) pyridine iron(II) complexes
文献类型：期刊论文
| 作者 | Minaev, Boris1,2,3; Baryshnikova, Alina3; Sun, Wen-Hua1,2
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| 刊名 | JOURNAL OF ORGANOMETALLIC CHEMISTRY
 |
| 出版日期 | 2016-06-01 |
| 卷号 | 811页码:48-65 |
| 关键词 | Ethylene polymerization Spin-catalysis Spin-orbit coupling Bis(imine)pyridyl iron(II) complexes Quantum-chemical calculations Brookhart-Gibson catalytic cycle |
| 英文摘要 | The general concept of spin-dependent polyethylene polymerization by the bis(imino) pyridine iron(II) complexes is presented. It is stressed that the driving force of ethylene polymerization in the presence of bis(imino)pyridyliron(II) is a high exothermic effect of the monomer binding to the catalyst in all three low-lying spin states. The origin of low activation barrier in termination reaction between the initial monomolecular ethylene and the growing polyethylene chain corresponds to the energy decreasing of the "ethylene-catalyst" high-spin state complex which correlates directly with the targeted low-spin products through intersystem crossing. The applicability of the spin-catalysis concept to the Brookhart-Gibson catalytic scheme is described in this work on the basis of the detailed analysis of previously published theoretical results of Ziegler's and Morokuma's groups and of recent experimental achievements. The role of the axial-equatorial isomerization in spin-catalysis of Brookhart-Gibson type is discussed in details in connection with the main mechanistic problem of ethylene catalytic polymerization - competition between chain propagation and beta-hydrogen atom transfer termination. The original part of review constitutes the calculation of spin-orbit coupling matrix elements in the Brookhart-Gibson catalytic cycle and the discussion of external magnetic field effect on ethylene polymerization. (C) 2016 Elsevier B.V. All rights reserved. |
| 收录类别 | SCI |
| 语种 | 英语 |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/36054]  |
| 专题 | 化学研究所_工程塑料实验室 |
| 作者单位 | 1.Chinese Acad Sci, Inst Chem, Key Lab Engn Plast, Beijing 100190, Peoples R China 2.Chinese Acad Sci, Inst Chem, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China 3.Bohdan Khmelnitsky Natl Univ, Dept Organ Chem, UA-18031 Cherkassy, Ukraine |
| 推荐引用方式 GB/T 7714 | Minaev, Boris,Baryshnikova, Alina,Sun, Wen-Hua. Spin-dependent effects in ethylene polymerization with bis(imino) pyridine iron(II) complexes[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY,2016,811:48-65. |
| APA | Minaev, Boris,Baryshnikova, Alina,&Sun, Wen-Hua.(2016).Spin-dependent effects in ethylene polymerization with bis(imino) pyridine iron(II) complexes.JOURNAL OF ORGANOMETALLIC CHEMISTRY,811,48-65. |
| MLA | Minaev, Boris,et al."Spin-dependent effects in ethylene polymerization with bis(imino) pyridine iron(II) complexes".JOURNAL OF ORGANOMETALLIC CHEMISTRY 811(2016):48-65. |
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来源：化学研究所
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