吡啶二亚胺Ni(Ⅱ)配合物的合成、晶体结构及其催化乙烯聚合的研究

高等学校化学学报 ›› 2005, Vol. 26 ›› Issue (7): 1215.

吡啶二亚胺Ni(Ⅱ)配合物的合成、晶体结构及其催化乙烯聚合的研究

范瑞清^1,3, 朱东升¹, 母瀛¹, 李光华², 冯守华²

1. 吉林大学超分子化学与材料教育部重点实验室,长春130012;
2. 吉林大学无机合成与制备化学国家重点实验室,长春130012;
3. 哈尔滨工业大学应用化学系,哈尔滨150001

收稿日期:2004-07-05 出版日期:2005-07-10 发布日期:2005-07-10
通讯作者: 母瀛(1958年出生),男,博士,教授,主要从事金属有机化学和均相催化研究.E-mail:ymu@mail.jlu.edu.cn E-mail:ymu@mail.jlu.edu.cn
基金资助:
国家自然科学基金(批准号:20374023)资助.

Synthesis, Characterization, Crystal Structures of Bis(imino)pyridyl Nickel Complexes and Their Catalytic Performance for Ethylene Polymerization

FAN Rui-Qing^1,3, ZHU Dong-Sheng¹, MU Ying¹, LI Guang-Hua², FENG Shou-Hua²

1. Key Laboratory for Supramolecular Structure and Materials of Ministry of Education;
2. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, China;
3. Depart_ment of Applied Chemistry, Harbin Institute of Technology, Harbon 150001, China

Received:2004-07-05 Online:2005-07-10 Published:2005-07-10

摘要/Abstract

摘要： 由三齿配体2,6-二[1-(2-甲基苯基亚胺)乙基]吡啶(L₁)和2,6-二[(1-苯基亚胺)乙基]吡啶(L₂)分别与NiCl₂.6H₂O在乙腈中反应,合成了两个吡啶二亚胺基氯化镍配合物L₁Ni(Ⅱ)Cl₂.CH₃CN(1)和L₂Ni(Ⅱ)Cl₂(2).通过元素分析、IR和¹HNMR对配体和配合物进行了结构表征,并测定了配合物1和2的晶体结构.X射线衍射分析结果表明,两个配合物均为五配位扭曲三角双锥构型,属单斜晶系,C_c空间群.配合物1的晶胞参数a=2.5783(5)nm,b=1.4843(3)nm,c=1.5866(3)nm;β=122.82(3),°V=5.1024(18)nm³,Z=4,R₁=0.0708,配合物2的晶胞参数a=1.5772(1)nm,b=0.8594(1)nm,c=1.5459(1)nm;β=103.27(1),°V=2.039(2)nm³,Z=4,R₁=0.0375.配合物1和2经MAO活化后对乙烯聚合表现出较低的催化活性.

关键词: 吡啶二亚胺基镍配合物, 晶体结构, 乙烯聚合

Abstract: Reactions of equimolar ratios of NiCl₂·6H₂O to the tridentate ligands 2,6-bis[1-(2-methyl-phenylimino)ethyl]pyridine(L¹) or 2,6-bis[(1-phenylimino)ethyl]pyridine(L²) in acetonitrile afford the five-coordinated complexes NiCl₂L¹·CH₃CN(1) and [NiCl₂L²·CH₃CN](2), respectively. All ligands and complexes were characterized by using elemental analysis, IR and ¹H NMR spectroscopy. The structures of complexes 1 and 2 were determined by single-crystal X-ray diffraction. Crystallographic studies on complexes 1 and 2 reveal both complexes to be pentacoordinated with geometries that can be best described as distorted trigonal bipyramidal. Complex 1 crystallizes in the monoclinic system, space group C_c, with a=2.578 3(5) nm, b=1.484 3(3) nm, c=1.586 6(3) nm; β=122.82(3)°, V=5.102 4(18) nm³, Z=4, R₁=0.070 8. Complex 2 belongs to monoclinic system with space group C_c, a=1.577 2(1) nm, b=0.859 4(1) nm, c=1.545 9(1) nm; β=103.27(1)°, (V=2.039 4(2) nm³,) Z=4, R₁=0.037 5. Complexes 1 and 2 exhibit lower catalytic activities for ethylene polymerization upon activation with MAO.

Key words: Bis(imino)pyridyl nickel complexes, Crystal structure, Ethylene polymerization

中图分类号:

O614

TrendMD:

范瑞清, 朱东升, 母瀛, 李光华, 冯守华. 吡啶二亚胺Ni(Ⅱ)配合物的合成、晶体结构及其催化乙烯聚合的研究. 高等学校化学学报, 2005, 26(7): 1215.

FAN Rui-Qing, ZHU Dong-Sheng, MU Ying, LI Guang-Hua, FENG Shou-Hua. Synthesis, Characterization, Crystal Structures of Bis(imino)pyridyl Nickel Complexes and Their Catalytic Performance for Ethylene Polymerization. Chem. J. Chinese Universities, 2005, 26(7): 1215.

参考文献

[1] Johns on L.K.,Killian C.M.,Brookhart M..J.Am.Ch em.Soc.[J],1995,117:6414_6415 [2] Kilian C.M.,Tempel D.J.,Johns on L.K.et al..J.Am.Chem.Soc.[J],1996,118:11664_11665 [3] Kilian C.M.,John son L.K.,Brookhart M..Organometall ics[J],1997,16:2005_2007 [4] Britovs ek G.J.P.,Gib son V.C.,Was s D.F..Angew.Ch em.Int.Ed.[J],1999,38:428_447 [5] LIU Chang-Kun(刘长坤),JIN Guo-Xin(金国新).Chem.J.Chines e Un iversi ties(高等学校化学学报)[J],2001,22(7):1233_1236 [6] Gib son V.C.,Spit z mes ser S.K..Chem.Rev.[J],2003,103:283_315 [7] Small B.L.,Brookh art M.,Bennet t A.M.A..J.Am.Chem.Soc.[J],1998,120:4049_4050 [8] Britovs ek G.J.P.,Gib son V.C.,Kimberley B.S.et al..J.Chem.Soc.,Chem.Commun.[J],1998:849_850 [9] Small B.L.,Brookh art M..J.Am.Ch em.Soc.[J],1998,120:7143_7144 [10] Brit ovs ek G.J.P.,Mast roian ni S.,Solan G.A.et al..Chem.Eu r.J.[J],2000,6:2221_2227 [11] Schmidt R.,Welch M.B.,Palack al S.J.et al..J.Mol.Cat al.A:Chem.[J],2002,179:155_173 [12] Gibson V.C.,Hum phries M.J.,Tel lmann K.P.et al..J.Chem.Soc.,Chem.Commun.[J],2001:2252_2253 [13] Abu-Surrah A.S.,Lappal ain en K.,Piironen U.et al..J.Organ om et.Chem.[J],2002,648:55_61 [14] Brit ovesk G.J.P.,Bruce M.,Gibs on V.C.et al..J.Am.Chem.Soc.[J],1999,121:8728_8740 [15] Small B.L.,Marcucci A.J..Organ omet allics[J],2001,20:5738_5744 [16] Feld man J.,McLain S.J.,Partt h as arat hy A.et al..Organ om et allics[J],1997,16:1514_1516 [17] Wang C.,Fri edrich S.,Grub bs R.H.et al..Organ omet allics[J],1998,17:3149_3151 [18] You nkin T.R.,Conn or E.F.,Henderson J.I.et al..Science[J],2000,287:460_462 [19] Zh on g J.Z.,Wang F..Act a Academiae Medicinae Jiangxi[J],1999,39:93_94 [20] SHELX T L N T Cryst al St ruct ur e Anal ysis Package,Version 5.10[CP],Bruk er A X S,Anal yt ical X-ray Syst em:Madi son,WI,1999