摘要
过渡金属与席夫碱配体形成的配合物以其多样的结构和广泛的用途愈来愈受到人们的重视。该类配合物在催化、生物活性及功能材料等领域都有广泛的应用前景。
本文首次合成了一种邻氨基苯甲酸衍生物——2-氨基-N-苯基-苯甲酰胺,并在此基础上合成了十二个新型席夫碱化合物以及不对称席夫碱——2-氨基-N-苯基-苯甲酰胺单缩水杨醛的同分异构体。选用其中两个化合物:2-氨基-N-苯基-苯甲酰胺双缩水杨醛(HL~1),2-氨基-N-苯基-苯甲酰胺缩 5-硝基水杨醛(HL~2),与过渡金属(Cr~(3+)、Mn~(2+)、Fe~(3+)、Co~(2+)、Ni~(2+)、Cu~(2+)、Zn~(2+)共合成配合物14种。分别是:[Cr(L~(la))_2]·ClO_4·2H_2O 1、Mn(L~(la))_2 2、[Fe(L~(la))_2]·ClO_4·H_2O 3、Co(L~(la))_2 4、Ni(L~(la))_2 5、Cu(L~(la))_2 6、Zn(L~(la))_2 7、[Cr(L~2)_2]·ClO_4·2H_2O 8、Mn(L~2)_2 9、[Fe(L~2)_2]·ClO_4·2H_2O 10、Co(L~2)_2 11、Ni(L~2)_2 12、[Cu(L~2)_2]·H_2O 13、Zn(L~2)_2 14。对上述配合物均进行了元素分析、红外光谱、紫外光谱以及荧光光谱等表征。根据实验事实,预测了配合物的性质。对部分配合物进行了热重分析测试,推测了配合物分解过程。
测定了2-氨基-N-苯基-苯甲酰胺双缩水杨醛(HL~1)和三种配合物[Fe(L~(la))_2]·ClO_4·H_2O3、[Fe(L~2)_2]·ClO_4·2H_2O 10、[Cu(L~2)_2]·H_2O 13的晶体结构。发现2-氨基-N-苯基-苯甲酰胺双缩水杨醛(HL~1)、[Fe(L~1)_2]·ClO_4·H_2O 3和[Fe(L~2)_2]·ClO_4·2H_2O 10通过氢键连接为一维链状超分子。配休HL~1和配体HL~2在配合物[Fe(L~(la))_2]·ClO_4·H_2O 3和[Fe(L~2)_2]·ClO_4·2H_2O 10中均为三齿配体。但是在配合物[Cu(L~2)_2]·H_2O 13中,由于Jahn-Teller效应和配体的空间位阻作用,一分子的配体以两齿形式和Cu(Ⅱ)进行配位,形成五配位的化合物。
The coordination compounds, synthesized with transition metal and Schiff-bases as raw materials, are more and more important for their various structures and extensive uses. The applied foreground of these compounds will be extensive in the field of catalysis, bioactivity and material etc. Among which, it is dramatically interesting that the complexes use as the polyethylene catalysis.
In this paper, a new o-amino benzoic acid derivative, 2-amino-N-phenyl-benzamide, has been obtained. And twelve new asymmetric Schiff bases containing 2-amino-N-phenyl-benzamide have been synthesized and characterized as well as an isomeric compound of 2-(2-hydroxy-benzylideneamino)-N-phenyl-benzamide. Two of them, the isomeric compound of 2-(2-hydroxy-benzylideneamino)-N-phenyl-benzamide(HL1) and 2-(2-hydroxy-5-nitryl-benzyl-ideneamino)-N-phenyl-benzamide(HL2), are used to synthesize the complexes with transition metal ions(Cr3+, Mn2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+), and fourteen complexes are achieved. [Cr(L1a)2].ClO4.2H2O1, Mn(Lla)22, [Fe(Lla)2].ClO4.H2O3, Co(Lla)24, Ni(Lla)25, Cu(Lla)26, Zn(Lla)27, [Cr(L2a)2].ClO4.2H2O8, Mn(L2)29, [Fe(L2)a].ClO4.2H2O 10, Co(L2)2 11, Ni(L2)212, [Cu(L2)2].H2O13, Zn(L2)214.
These complexes are all determined by elemental analysis, infrared spectra, UV spectra and fluorescence spectra. The properties of these compounds are forecasted by experiment facts. The thermal decomposition of some complexes has been investigated by TG-DSC. Their thermal decomposition processes have been presumed by experiment facts
The crystal structures of one ligand and three complexes have been determined. They are HL1.C2H6OH, [Fe(Lla)2].ClO4.H2O 3, [Fe(L2)2].ClO4.2H2O 10 and [Cu(L2)2].H2O 13. In HL1.C2H6OH, compound 3 and 10, it has been found that all compounds were formed
one-dimensional chain supramolecules combined by intermolecular hydrogen bonds. The ligand HL1 performs as a tridentate ligand in complex 3 as well as HL2does in complex 10. In complex 3 and 10, the central Fe(III) ions are in six coordination environment. However, one of the ligands is acted as a bidentate ligand in compound 13 because of the Jahn-Teller effect and the steric interference of the ligand. Therefore, the central Cu(II) ions are in five coordination environment.
引文
1 游效曾.孟庆金,韩万书等.配位化学进展,北京:高等教育出版社.2000
2 魏丹毅,李冬成,姚克敏等.无机化学学报,1998,14(2):209-215
3 袁淑军,蔡春,吕春绪等.应用化学,2003,20(3):278-281
4 何星存,蔡沛祥,莫金垣等.催化学报,2000,19(1):9-13
5 姚克敏,李冬成,沈联芳等.化学学报,1993,51:677-682
6 唐波,刘阳.梁芳珍.化学学报,2000,58(8):1031-1036.
7 叶勇,胡继明.曾云鹗等.无机化学学报,2000,16(6):951-959
8 蒋毅民,张淑华.徐庆等.化学学报,2003,61(4):573-577
9 Jiang Yaozhong, Zhou Zhiangge, Hu Wenhao, et al. Tetrahedron: Asymmetry, 1995, 6(2): 405-408
10 Patani G A, Lavoie F.. J Chem Review, 1996, 96:3147-3160
11 赵国锋,杨华铮.化学通报,1995,(6):34-35
12 杨光富,赵国锋,陆荣健等.中国科学B辑,1998,28(3):283-289
13 于文锦,李锦州,李刚.无机化学学报,1999,15(5):657-661
14 牛瑞民,朱小蓉,孙真荣等.光学学报,2003,23(1):17-21
15 吕绪良,许卫东,崔传安等.解放军理工大学学报,2000,1(6):54-57
16 Tamotsu Inabe, Isabelle Gautier-Luneauetal. Bull Chem Soc Jpn, 1991,64:801
17 崔学柱,冯绪胜,胡清萍等.化学物理学报,1999,12(3):370-375
18 Owiny D, Parking S, Ladipo F T, et al. Journal of Organometallic Chemistry. 1992,678(1): 134-141
19 蔺彬彬,仇永清,苏忠民等,高等学校化学学报,2001,22(9): 1551-1554
20 Agarwal S K, Tandon J P.Synth React Inorg-Met-Org Chemistry, 1974, 4:387-401
21 Srivastava T N, Chauhan A K S. Synth React lnorg-Met-Org Chemistry, 1977, 7(4): 373-385
22 Hamada T, Fukuda T, Imanishi H, et al. Tetrahedron, 52(2): 515-530
23 Kervinen K, Korpi H, Leskela, Markku, et al. Joumal of Molecular Catalysis A: Chemical, 2003, 203(1): 9-19
24 Pui A, Berdan L, Morgenstem-Badarau I, Gref A, et al. Inorganica Chimica Acta, 2001, 320(2): 167-171
25 Halligudi S B, Kala Raj N K, Deshpande S S, et al. Journal of Molecular Catalysis A: Chemical, 2000, 157(2), 9-14
26 孙伟,陈敏东,复春谷等.分子催化,2002,16(2):144-147
27 彭云贵,冯小明,于斌等.高等学校化学学报,2001,22(2):223-227
28 Qian Mingxing, Wang Mei, He Ren, et al.催化学报,2000,21(2): 99-100
29 Elder R C. Aust J Chem, 1978,31:35
30 Atkins R, Brewer G. Kokot G, et al. Inorg Chem, 1985,24:127
31 孟庆金,王瑞雪,步修仁等.高等学校化学学报,1990,11(10):1126-1128
32 姚克敏,李冬成,沈联芳等.化学学报,1993,51:677-682
33 杨名辉,李新生,陈义朗等.化学试剂,2002,24(5):226-270
34 寇兴明,曾宪诚.无机化学学报,2002,18(9):892-896
35 Vigato P A, Fenton D E. Inorg Chim Acta, 1987, 139:39
36 Agarwala R G. J Inorg Nucl Chem, 1973, 35:653-655
37 张文兴,于耕霖.化学学报,1986.44:1261
38 Mahapatra B B, Dash S S, Pujari S K. J Indian Chem Soc, 1980, 57:95
39 张宝龙,季振平,萧文锦等.高等学校化学学报,1992.13(5):580
40 Hodnett E M, Dunn W J. J Med Chem, 1970, 13:768
41 陈德余,张义建,张平等.应用化学,2000,17(6):607-610
42 张建民,李瑞芳,刘树祥等.无机化学学报,1999,15(4):493-496
43 叶勇.胡继明,曾云鹗等.无机化学学报,2000,16(6):951-958
44 Younkin T R, Connor E F, Grubbs R H, et al. Science. 2000, 287:460
45 Shigekazu Matsui, Terunori Fujita. Catalysis Today, 2001,66:63-73
46 Johnson L K, Killian C M, Brookhart M, et al. J Am Chem Soc, 1995, 117:6414-6415
47 Small B L, Brookhart M, Bennett A M A, et al. J Am Chem Soc, 1998, 120:4049-4050
48 Britovsek G J P,Bruce M, Gibson V C, et al. J Am Chem Soc, 1999, 121:8727-8740
49 Small B L, Brookhart M. J Am Chem Soc, 1998, 120:7143-7144
50 李琛,张维萍,姚小泉等.催化学报,2000,21(3):289-291
51 仇敏,刘国生,姚小泉等.催化学报,2001,22(1):77-80
52 Li Zhengning, Zheng Zhuo, Wan Boshun, et al.Journal of Molecular Catalysis A: Chemical, 2001,165(2), 67-71
53 Wang Hongwang, Sun Wei, Xia Chungu. Journal of Molecular Catalysis A: Chemical, 2003, 206(2): 199-203
54 Li Zhengning, Liu Guosheng, Zheng Zhou, et al. Tetrahedron, 2002, 56(37): 7187-7191
55 彭清静,傅伟吕,邹晓勇等.化学世界,2001,10:539-541
56 范谦,黎耀忠,程克梅等.四川大学学报(自然科学版).2001,38(2):230-234
57 Theriot L J. Carlisle G O, Hu H J. J Inorg Nucl Chem, 1969, 31: 2841
58 徐汉红,朱传方.化学通报,2000,8:15-20
59 Hadjoudis E, Milia F, et al. Chemical Physics, 1991, 156:149-155
60 Hadjoudis E, Vittorakis M, et al. 1987, 43(7): 1345-1360
61 Ahmed M Donia, Hanaa A EI-Boraey. Transition Met Chem, 1993, 18:315~318
62 Ahmed M Doina, S A Amer, et al. Thermochimica Acta, 1989, 137:189-196
63 Ahmed M Donia, EI-Zeiny M Ebid. Thermochimica Acta, 1988, 131 : 1-6
64 Naohide Matsum oto, Kazuhiro Kimoto, et al. Bull Chem Soc Jpn, 1984, 57:3307-3311
65 宁永成.有机化合物结构坚定与有机光谱学,北京:科学出版社,2000
66 黄量、于德泉.紫外光谱在有机化学中的应用,北京:科学出版社,1998
67 陈国珍.荧光分析法,北京:科学出版社,1975
68 Oyaizu Kenichi, Dewi Eniya Listiani, Tsuchida Eishun. Inorganica Chimica Acta, 2001, 321: 205-208
69 Noveron Juan C., Herradora Ruth, Olmstead Marilyn M., et al. Inorganica Chimica Acta, 1999, 285: 269-276
70 史启祯,赵凤起,阎海科,等.热分析动力学余热动力学,西安:陕西科学技术出版社,2001
71 中本一雄.无机和配位化合物的红外和拉曼光谱,北京:化学工业出版社,1978
72 常建华,董绮功.波谱原理及解析,北京:科学出版社,2001
73 Wang Jun, Bei Fenli, Yang Xuijie, et al. Joumal of molecular structure, 2002, 643:129-133
74 Elerman Y., Elmali A., ?zbey S. Acta Crystallogr, 1998, C54:549-555
75 ?nver H., Durlu Nuri T. J. Chem. Crystallogr, 2001,31: 479-486
76 Francisco Hueso-Ure?a, Antonio L. Pe?as-Chamorro, Miguel N. Moreno-Carretero, et al. Polyhedron, 1999, 18:2205-2210