2-亚胺-1,10-邻二氮杂菲铁(Ⅱ)类催化剂活性与中心金属原子净电荷的关系

高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (2): 343.

2-亚胺-1,10-邻二氮杂菲铁(Ⅱ)类催化剂活性与中心金属原子净电荷的关系

段宝根¹, 孔滨¹, 孙文华², 杨小震¹

1. 中国科学院化学研究所, 北京分子科学国家实验室, 高分子物理与化学国家重点实验室,
2. 工程塑料重点实验室, 北京 100190

收稿日期:2009-05-20 出版日期:2010-02-10 发布日期:2010-02-10
通讯作者: 杨小震, 男, 研究员, 博士生导师, 主要从事高分子计算机模拟研究. E-mail: yangx@iccas.ac.cn
基金资助:
国家自然科学基金(批准号: 20674090)资助.

Relationship Between Catalytic Activity and Metal Atom Net Charge of Iron Complex Bearing 2-Imino-1,10-phenanthrolinyl Ligand

DUAN Bao-Gen¹, KONG Bin¹, SUN Wen-Hua², YANG Xiao-Zhen^1*

1. Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Polymer Physics and Chemistry,
2. Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

Received:2009-05-20 Online:2010-02-10 Published:2010-02-10
Contact: YANG Xiao-Zhen. E-mail: yangx@iccas.ac.cn
Supported by:
国家自然科学基金(批准号: 20674090)资助.

摘要/Abstract

摘要：

应用金属原子净电荷相关性(MANCC)方法研究了铁(Ⅱ)类催化剂活性. 取代基的电子效应占主导作用的催化剂, 活性与中心金属原子净电荷有较好的相关性. 当取代基呈供电子效应时, 催化剂活性随着电荷的增大而升高, 当取代基呈吸电子效应时, 催化剂活性随着电荷的增大而降低. 在此基础上推测烯烃聚合反应催化过程中可能存在两种不同的活性中心, 一种是[LFe—R]⁺, 另一种是[LFe—R]²⁺或[Fe(Cl)RL]⁺. 当取代基的电子效应和空间效应均对活性有影响时, 发现催化剂的两卤素净电荷差值越小, 催化活性越强.

关键词: 分子力学; 电荷平衡; 乙烯齐聚; 催化活性

Abstract:

The metal atom net charge correlation(MANCC) method was used to study catalytic activities of a series of asymmetric iron complexes bearing 2-imino-1,10-Phenanthroliyl ligands for ethylene oligomerization. If the catalytic activity is influenced mostly by electronic effect, it has a good correlation to the metal atom net charge. In general, catalytic activities of iron complexes bearing electron-donating alkyl groups increase with the net charges increasing. On the contrary, with the net charges increasing, catalytic activities decrease while the complexes contain electron-withdrawing halogen groups. Based on the above results, we speculated that two different activated centers probably existed in ethylene oligomerization which are [LFe—R]⁺ and [LFe—R]²⁺([Fe(Cl)RL]⁺). When both the electronic and steric effects of coordinative ligand affect the catalytic activity, the charge difference on the two halogen atoms was correlated with it. And it is found that the cataly-tic activity is improved corresponding to the smaller charge difference.

Key words: Molecular mechanics; Charge equilibration; Ethylene oligomerization; Catalytic activity

TrendMD:

段宝根, 孔滨, 孙文华, 杨小震. 2-亚胺-1,10-邻二氮杂菲铁(Ⅱ)类催化剂活性与中心金属原子净电荷的关系. 高等学校化学学报, 2010, 31(2): 343.

DUAN Bao-Gen, KONG Bin, SUN Wen-Hua, YANG Xiao-Zhen*. Relationship Between Catalytic Activity and Metal Atom Net Charge of Iron Complex Bearing 2-Imino-1,10-phenanthrolinyl Ligand. Chem. J. Chinese Universities, 2010, 31(2): 343.

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