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1、中南民族大学 硕士学位论文 新型水杨酰肼衍生物镍配合物的合成、表征及其模拟脲酶的催 化活性研究 姓名：冯晓红 申请学位级别：硕士 专业：有机化学 指导教师：金龙飞 2011-05-10 6 摘 要 本文合成了四种新型的水杨酰肼类 化合物 N- 氯乙酰基水杨酰肼 (H3cashz)、N- 氯乙酰基- 5- 氯水杨酰肼 (H3cacshz)、N- 氯乙酰基- 5- 溴水杨酰肼 (H3cabshz)、4- 水杨酰基氨基硫脲 (H3st)，以及相应的金属镍配合物，并采用 红外光谱、1H 和 13C 核磁共振谱以及元素分析等方法对化合物进行了表征。 对其中培养得到的单晶进行了 X- 射线单晶衍射结构分析
2、。同时，还对金属镍 配合物的模拟脲酶催化活性进行了研究。 对四种配合物Ni3(C9H6N2O3Cl)2(C3H7NO)2(C5H5N)2, Ni3(C9H5N2O3Cl2)2 (C3H7NO)2(C5H5N)2 2(C3H7NO),Ni3(C9H6N2O3BrCl)2(C3H7NO)2(C5H5N)2 2(C3H7NO)和Ni3(C8H6N3O2S)2 (C5H5N)2分别进行了单晶衍射测定，其结构 参数如下： 配合物Ni3(C9H6N2O3Cl)2(C3H7NO)2(C5H5N)2为三核配合物，属单斜晶 系， 空间群 P2(1)/n， 晶胞参数a = 11.688(2) , b = 9.58
3、31(17) , c = 17.226(3) , a = 90, = 92.015(4), ? = 90, V = 1928.2(6) 3, Z = 2, R1 = 0.0544，wR2 = 0.0919。 对配合物Ni3(C9H5N2O3Cl2)2(C3H7NO)2(C5H5N)2 2(C3H7NO) 为三核配 合物，属三斜晶系，空间群 P- 1，晶胞参数 a = 9.2654(11) , b = 13.7345(16) , c = 20.413(2) , a = 72.078(2), = 87.002(2), ? = 84.917(2), V = 2461.1(5) 3, Z = 2, R
4、1 = 0.0815, wR2 = 0.1804。 配合物Ni3(C9H6N2O3BrCl)2(C3H7NO)2(C5H5N)2 2(C3H7NO)为三核配合 物，有单斜晶系和三斜晶系两种晶型。其中，单斜晶系晶体空间群 P2(1)/n，晶 胞参数 a = 20.88(2) , b = 9.327(9) , c = 26.95(3) , a = 90, = 109.83(2), ? = 90, V = 4938(9) 3, Z = 4, R1 = 0.0506, wR2 = 0.1246; 三斜晶系晶体空间群 P- 1，晶胞参数 a = 9.275(9) , b = 13.777(11) , c
5、 = 20.466(19) , a = 71.671(16), = 86.819(15), ? = 84.710(19), V = 2471(4) 3 , Z = 2, R1 = 0.0566, wR2 = 0.1157。 配合物Ni3(C8H6N3O2S)2(C5H5N)2为三核配合物，晶体 A 属单斜晶系，空 间群 P2(1)/c，晶胞参数 a = 15.040(2) , b = 14.3593(19) , c = 6.2476(8) , a = 90, = 98.063(2), ? = 90, V = 1335.9(3) 3 , Z = 2, R1 = 0.0484, wR2 = 0.0
6、958。 对所合成的配合物进行了催化活性研究，结果发现这四种配合物对尿素分 7 别具有一定的催化作用，其中的Ni3(C9H6N2O3Cl)2(C3H7NO)2(C5H5N)2催化作 用相对最强， Ni3(C9H6N2O3BrCl)2(C3H7NO)2(C5H5N)2 2(C3H7NO)的催化作用 相对最弱。 关键词：水杨酰肼衍生物；镍配合物；晶体结构；模拟脲酶；催化活性 ABSTRACT In this thesis, four complexes containing Nchloroacetylsalicylhydrazide (H3cashz), Nchloroacetyl5chloros
7、alicylhydrazide (H3cacshz), Nchloroacetyl 5bromosalicylhydrazide (H3cabshz) and 4salicyloyl thiosemi carbazide (H3st) have been synthesized. IR, 1H NMR、13C NMR and Elemental analysis were used to characterize the compounds. XRay single crystal diffraction measurements were used to characterize the c
8、rystals. And the catalytic activities of all the compounds have been studied. XRay single crystal diffraction measurements were used to characterize the crystals of Ni3 (C9 H6 N2 O3 Cl)2(C3 H7 NO)2(C5 H5 N)2, Ni3 (C9 H5 N2 O3 Cl2 )2(C3 H7NO)2(C5 H5 N)22(C3 H7 NO), Ni3 (C9 H6 N2 O3 BrCl)2 (C3 H7 NO)2
9、(C5 H5 N)22(C3 H7NO) and Ni3(C8 H6 N3 O2 S)2(C5 H5 N)2. The crystallographic data are as follows: The complex of Ni3(C9H6N2O3Cl)2(C3H7NO)2(C5H5N)2 is a trinuclear cluster which has been determined in the crystal system monoclinic, space group P2(1)/n, with a = 11.688(2) , b = 9.5831(17) , c = 17.226
10、(3) , = 90, = 92.015(4), = 90, V= 1928.2(6) 3 , Z = 2, R1 = 0.0544, wR2 = 0.0919. The complex of Ni3(C9H5N2O3Cl2)2(C3H7NO)2(C5H5N)22(C3 H7NO) is a trinuclear cluster which has been determined in the crystal system triclinic, space group P1, with a = 9.2654(11) , b = 13.7345(16) , c = 20.413(2) , = 7
11、2.078(2), = 87.002(2), = 84.917(2), V = 2461.1(5) 3 , Z = 2, R1 = 0.0815，wR2 = 0.1804. The complex of Ni3(C9H6N2O3BrCl)2(C3H7NO)2(C5H5N)22(C3H7 NO) is trinuclear cluster which has been determined in the crystal system monoclinic and Triclinic. The crystal system monoclinic space group P2(1)/n, with
12、a = 20.88(2) , b = 9.327(9) , c = 26.95(3) , = 90, = 109.83(2), = 90, V = 4938(9) 3, Z = 4, R1 = 0.0506, wR2 = 0.1246;The crystal system triclinic space group P1, with a = 9.275(9) , b = 13.777(11) , c = 20.466(19) , = 71.671(16), = 86.819(15), = 84.710(19), V = 2471(4) 3 , Z = 2, R1 = 0.0566, wR2 =
13、 0.1157. The complex of Ni3(C8H6N3O2S)2(C5H5N)2 is a trinuclear cluster which has been determined in the crystal system monoclinic, space group P2(1)/c, with a = 15.040(2) , b = 14.3593(19) , c = 6.2476(8) , = 90, = 98.063(2), = 90, V = 1335.9(3) 3 , Z = 2, R1 = 0.0484, wR2 = 0.0958. The catalytic a
14、ctivity for the hydrolysis of urea of all the complexes have been determined, the results show that all of four complexes have certain catalytic activity. Among the four complexes, Ni3(C9H6N2O3Cl)2 (C3H7NO)2(C5H5N)2 has relatively strongest catalytic activity, Ni3(C9H6 N2O3BrCl)2(C3H7NO)2(C5H5 N)22(
15、C3H7NO) has the weakest catalytic activity. Key Words：derivatives of salicylhydrazide；nickel complexes；crystal structure； simulation of urease；catalytic activity 2 中南民族大学 学位论文原创性声明 本人郑重声明：所呈交的论文是本人在导师的指导下独立进行研究所 取得的研究成果。除了文中特别加以标注引用的内容外，本论文不包含任 何其他个人或集体已经发表或撰写的成果作品。对本文的研究做出重要贡 献的个人和集体，均已在文中以明确方式标明。本人完全意识到本声明的 法律后果由本人承担。 作者签名： 日期： 年 月 日 学位论文版权使用授权书 本学位论文作者完全了解学校有关保留、使用学位论文的规定，同意 学校保留并向国家有关部门或机构送交论文的复印
