2,6-吡啶二亚胺基锰(Ⅱ)配合物的合成、晶体结构及催化性能

高等学校化学学报 ›› 2011, Vol. 32 ›› Issue (6): 1239.

2,6-吡啶二亚胺基锰(Ⅱ)配合物的合成、晶体结构及催化性能

范瑞清¹, 袁国辉², 丁晓东¹, 陈劼³, 杨玉林¹

1. 哈尔滨工业大学化学系,
2. 化工学院, 哈尔滨 150001;
3. 大庆油田有限责任公司勘探开发研究院, 大庆163712

收稿日期:2010-11-04 修回日期:2011-03-25 出版日期:2011-06-10 发布日期:2011-05-10
通讯作者: 范瑞清;杨玉林 E-mail:fanruiqing@163.com;ylyang@hit.edu.cn
基金资助:
国家自然科学基金(批准号： 21071035, 20971031), 黑龙江省自然科学基金重点项目(批准号: ZD201009)和哈尔滨市科技创新人才基金(批准号: 2010RFQXG017)资助.

Synthesis, Characterization , Crystal Structures and Catalytic Performance of 2,6-Bis(imino)pyridyl Manganese Complexes

FAN Rui-Qing^1*, YUAN Guo-Hui², DING Xiao-Dong¹, CHEN Jie³, YANG Yu-Lin^1*

1. Department of Chemistry,
2. School of Chemical Engineering & Technology, Harbin Institute of Technology, Harbin 150001, China;
3. Daqing Oilfield Company Ltd. Exploration and Development Research Institute, Daqing 163712, China

Received:2010-11-04 Revised:2011-03-25 Online:2011-06-10 Published:2011-05-10
Contact: FAN Rui-Qing;YANG Yu-Lin E-mail:fanruiqing@163.com;ylyang@hit.edu.cn
Supported by:
国家自然科学基金(批准号： 21071035, 20971031), 黑龙江省自然科学基金重点项目(批准号: ZD201009)和哈尔滨市科技创新人才基金(批准号: 2010RFQXG017)资助.

摘要/Abstract

摘要： 由三齿含氮配体2,6-二[1-(2,6-二甲基苯基亚胺)乙基]吡啶(L1)、2,6-二[1-(2,6-二乙基苯基亚胺)乙基]吡啶(L2)和2,6-二[1-(2,4,6-三甲基苯基亚胺)乙基]吡啶(L3)分别与MnCl2?4H2O在乙腈中反应，合成了三个新的具有较大空间位阻2,6-吡啶二亚胺基氯化锰配合物L1Mn(II)Cl2?CH3CN(Mn1), L2Mn(II)Cl2?CH3CN(Mn2)和L3Mn(II)Cl2?CH3CN(Mn3). 采用元素分析、红外光谱和单晶X射线衍射对配合物Mn1–Mn3进行了结构表征. 单晶X射线衍射分析结果表明，三个配合物均为五配位扭曲三角双锥构型，属单斜晶系. 配合物Mn1属于P21/n空间群，晶胞参数a = 1.3304(3) nm, b = 1.4864(3) nm, c = 1.4423(3) nm; β = 108.41(3)?, V = 2.7063(9) nm3, Z = 4, F(000) = 1116 , R1 = 0.0465. 配合物Mn2属于P21/c空间群，晶胞参数a = 1.2919(1) nm, b = 1.5283(1) nm, c = 1.6362(1) nm; β = 99.27(1)?, V = 3.1883(3) nm3, Z = 4, F(000) = 1244, R1 = 0.0599. 配合物Mn3属于P21/n空间群, a = 1.4542(3) nm, b = 1.5083(3) (1) nm, c = 1.4646(3) nm; β = 112.56(3)?, V = 2.9667(10) nm3, Z = 4, F(000) = 1180, R1 = 0.0627. 并研究了配合物Mn1–Mn3在有机硼助催化剂[Ph3C]+[B(C6F5)4]-活化后对乙烯聚合的催化性能.

关键词: 2,6-吡啶二亚胺基锰配合物, 晶体结构, 乙烯聚合

Abstract: Reactions of equimolar rations of MnCl2?4H2O and the tridentate ligands 2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridine (L1), 2,6-bis[1-(2,6-diethy phenylimino)ethyl]pyridine (L2), and 2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridine(L3) in acetonitrile afford the five-coordinated complexes L1Mn(II)Cl2?CH3CN(Mn1), L2Mn(II)Cl2?CH3CN(Mn2) and L3Mn(II)Cl2?CH3CN(Mn3), respectively. All complexes were characterized using elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystallographic studies on complexes Mn1–Mn3 reveal three complexes to be pentacoordinate with geometries that can be best described as distorted trigonal bipyramidal. Mn1 crystallizes in the monoclinic system, space group P21/n, with a = 1.3304(3) nm, b = 1.4864(3) nm, c = 1.4423(3) nm; β = 108.41(3)?, V = 2.7063(9) nm3, Z = 4, F(000) = 1116 , R1 = 0.0465. Mn2 belongs to monoclinic system with space group P21/c, with a = 1.2919(1) nm, b = 1.5283(1) nm, c = 1.6362(1) nm; β = 99.27(1)?, V = 3.1883(3) nm3, Z = 4, F(000) = 1244, R1 = 0.0599. Mn3 belongs to monoclinic system with space group P21/n, with a = 1.4542(3) nm, b = 1.5083(3) (1) nm, c = 1.4646(3) nm; β = 112.56(3)?, V = 2.9667(10) nm3, Z = 4, F(000) = 1180, R1 = 0.0627. Complexes Mn1–Mn3 exhibit lower catalytic activities for ethylene polymerization after activation with cocatalysts of [Ph3C]+[B(C6F5)4]-.

Key words: 2,6-Bis(imino)pyridyl manganese complexes, crystal structure, Ethylene polymerization

TrendMD:

范瑞清, 袁国辉, 丁晓东, 陈劼, 杨玉林. 2,6-吡啶二亚胺基锰(Ⅱ)配合物的合成、晶体结构及催化性能. 高等学校化学学报, 2011, 32(6): 1239.

FAN Rui-Qing*, YUAN Guo-Hui, DING Xiao-Dong, CHEN Jie, YANG Yu-Lin*. Synthesis, Characterization , Crystal Structures and Catalytic Performance of 2,6-Bis(imino)pyridyl Manganese Complexes. Chem. J. Chinese Universities, 2011, 32(6): 1239.

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