摘要
本论文利用异烟酰肼、水杨酰肼与丁二酮设计合成稀土双Schiff碱配合物,最终得到了其中三个配合物的晶体,解析了它们的单晶结构:
(1)首次合成了以丁二酮双缩异烟肼双Schiff碱为配体的稀土配合物[(LaL)(NO_3)_3(CH_3CH_2OH)]·(CH_3CH_2OH)_3,解析了其单晶结构,进行了IR谱分析和乙醇溶液的紫外-可见吸收光谱分析,并讨论了晶体内的弱相互作用。
(2)以水杨酰肼、丁二酮、硝酸铈和硝酸镧为原料,合成了两个十一配位的配合物,这是首次得到的以丁二酮双缩水杨酰肼双Schiff碱为配体的金属配合物,解析了其单晶结构,进行了IR谱分析和乙醇溶液的紫外-可见吸收光谱分析。
上述三个酰腙类稀土配合物单晶解析的结果表明,这几个配合物的配位数都是十一,均高于较常见的8和9,配合物中都有溶剂分子参与了配位。较高的配位数与本文所设计合成的双酰腙配体有关,两个配体上的羰基氧原子和Schiff碱亚胺上的氮原子可以向同一个金属原子配位,在较小的空间可提供较多的配位原子,使更多原子参与配位成为可能。由于稀土元素具有基本相同的外层电子结构,故以丁二酮双缩水杨酰肼为配体的镧和铈的两个配合物的结构和部分性质基本相同,而丁二酮双缩异烟肼镧的配合物与本课题组所得到的丁二酮双缩异烟肼铈的配合物在结构和红外等性质上也很相似。
Isonicotinoyl hydrazine, salicyloyl hydrazine and 2,3-butanedione were used to synthesise rare earth bis-Schiff base complexs in this dissertation. Three new complexes were finally synthesized and structurally characterized.
(1) A crystalline complex [(LaL)(NO_3)_3(CH_3CH_2OH)]·(CH_3CH_2OH)_3 was synthesized by reaction of 2,3-butanedione, isonicotinoyl hydrazine and La(NO_3)_3·6H_2O in CH_3CH_2OH. The complex was characterized by IR and UV spectral methods and X-ray single crystal diffraction.
(2) Two crystalline complexs were synthesized by reaction of 2,3-butanedione, salicyloyl hydrazine and La(NO_3)_3·6H_2O or Ce(NO_3)_3·6H_2O in CH_3CH_2OH. The complexes were characterized both by IR and UV spectral methods and X-ray single crystal diffraction.
The above comlexes are similar in structures and properties. They were eleven-coordinate. This coordination number is higher than ordinary ones of 8 or 9. This can be attributed to the characteristics of the dihydrazone ligands.
引文
[1]稀土配位化学,黄春辉,北京:科学出版社,1997
[2]Dutt.K.K., Nag.K., One-dimensional coordination polymers-applications to material science, Coord. Chem. Rev., 1968, 10(1-2): 23~32
[3]Meek D.W., Strauad D.K., Drago R.S., Transition metal ion complex of dimethyl sulfoxide, J. Am. Chem. Soc., 1990, 88: 6013~6016
[4]Rowland R.S., Taylor R., Inermolecular nonbonded contact distances in organic crystal structures: comparison with distances from van der Waals Radii, J. Phys. Chem., 1996, 100: 384~7391
[5]Desiraju G. R., Hydrogen bridges in crystal engineering: interactions without Borders, Acc. Chem. Res., 2002, 35: 565~573
[6]Zhang X.Y., Zhang Y.J., Molecular structures with a macrocyclic ligand, Chinese. J. Struc. Chem., 2003, 22(3): 293~296
[7]Li S.L., Chen S.H., Li S.B., Investigation on some Schiff bases as HCl corrosion inhibitor, Corrosion Science, 1999, 41: 1273~1287
[8]Qu Z., Wu X., Self-assembled monolayer of Schiff base on complexes faces, Corrosion, 2001, 57(3): 195~201
[9]Rao T.R., Srivastava M.R., Synthesis and spectral studies of some lanthanide metal chelates of an unsymmetrical tridentate Schiff base, Synth. React. Inorg. Met-Org. Chem., 1992, 22(10): 1551~1564
[10]Gang B.S., Choudhury M., Dixit R.,Determination of stability constants and thermodynamic parameters of complexes of diacetylmono(lepidyl)hydrazone(DALH) with lanthanides, Thermochimica Acta, 1989, 154: 213~218
[11]Yang Z.Y., Yang R.D., Li Q., Synthesis, characterization and biological activity of rare earth complexes of 1- phenyl-3-methyl-5-hydroxy-4-pyrazolyl phenyl ketene isonicotinoyl hydrazone , Synth. React. Inorg. Met-Qrg. Chem., 1999, 29(2): 205~214
[12]ZhaoG., MaY.X., Coordination complexes of acetylferrocene-m-nitrobenzoyl hydrazone with lanthanides, Polyhedron, 1991, 10(18): 2185~2189
[13]Bu X.D., Du M.,Zhang L., Thomas Clifford, Novel homobinuclear lanthanide(III) complexes with isonicotinoyl hydrazone: synthesis and coordination chemistry, Inorg. Chim. Acta., 2000, 308: 143~149
[14]Paschalidis D.G., Tossidis1 A., Gdaniec M.,Synthesis,characterization and spectra of Lanthanide(III) hydrazone complexes the X–ray molecular structures of the erbium(III) complex and the ligand, Polyhedron, 2000, 19: 2629~2637
[15]李宁,姚克敏,娄开炎,La(III)、Y(III)与多甘醇醛缩氨基酸Schiff碱配合物的合成及其固体高分辨13C NMR波谱,中国科学(B),999,29(5):450~455
[16]Siddiqi K., Tabassum S., Synth. React. Inorg. Met-org. Chem., 1991, 21(2): 217
[17]张秀英,张有娟,稀土在生物领域中应用研究进展,中国稀土学报,1999,17(增刊) :392~394
[18]Xiuying Zhang, Youjuna Zhang , Synthesis and Reactivity in Inorganic and Metal Organic Chemistry , 2000 ,30(1): 45~55
[19]杨军,席夫碱大环聚醚稀土配合物的光谱分析,广西化工,1998,27(3):53
[20]雷秀斌,季振平,萧文锦,稀土冠醚配合物的研究—稀土硝酸盐Schiff碱型大环配合物的合成和性质,高等学校化学学报,1990,11(6):565
[21]臧焰,王德松,王国雄,大环希夫碱稀土配合物的合成及表征,无机化学学报,1987,3(1):66
[22]Costes J P, Inorg. Chem. Acta,, 1998, 268 (1): 125
[23]吴静,姚克敏,直链醚席夫碱与Ln3+-Zn2+异双核配合物的合成和表征,中国稀土学报,1999,17(2):166~168
[24]张秀英,张有娟,我国Schiff碱稀土配合物的研究进展,化学研究与应用, 2002,14(3):9~13
[25]李冬成,姚克敏,曹美华,稀土元素与3,4-二羟基苯甲醛缩邻氮基苯甲酸配合物的合成和表征,应用化学,1993,10(3):81
[26]姚克敏,沈联芳,Ln(III)—Co (II)与双水杨醛缩乙二胺碱移和配合物的合成与波谱性质,应用化学,1998,5(5):11
[27]NairM.K., RadhakrishnanP.K., Synth. React. Inorg. Met-Org. Chem., 1995,25 (7):1077
[28] Vodkumar C.R., Radhakrishnan P.K., Synth. Met-Org. Chem., 1997 ,27(9) :1347
[29]魏丹毅,李冬成,姚克敏,稀土元素与丙氨酸希夫碱双核配合物的合成、表征及催化活性,无机化学学报,1998,14(2):209~203
[30]毕彩丰,范玉华等,水杨叉替乙二胺与稀土硝酸盐配合物的研究,稀土学报,1993,14(1):61
[31]Li Bin, Zhao Guoliang, Tang Guoqing, Synth. React. Inorg. Me-Org. Chem., 1991, 21 (9): 1387
[32]姚克敏,陈德余,王晓南,直链醚席夫碱钆配合物EPR特性及其溶剂效应,中国科学(B),1995,25(11):1144
[33]易国斌,陈德余,钆(III)天冬酰胺席夫碱配合物的EPR波谱,化学物理学报,1998,11(3):2671
[34]姚克敏,陈德余,封子先,四种席夫碱钆配合物EPR波谱研究中国科学(B), 1994,24(12):1252
[35]李彬,赵国良,刘国发,邻香兰素与二胺类双希夫碱镧配合物的合成,应用化学,1990,7(6):701
[36]张武,杜宝辉,王修然,含茂基及双水杨醛缩乙二胺基稀土有机配合物的合成,合成化学,1999 ,7(3):2331
[37]王耕霖,苗蓝,镧系元素十八元六氮大环配合物的研究,高等学校化学学报, 1984,5(3):2811
[38]李宁,姚克敏,娄开炎,La(III)、Y(III)与多甘醇醛缩氨基酸Schiff碱配合物的合成及其固体高分辨13C NMR波谱,中国科学(B),1999,29(5):450~455
[39]孔繁荣,宗瑞发,乔赤兵,某些稀土硝酸盐与一二亚水杨基乙二胺一二甲基亚砜三元配合物的合成和晶体结构,高等学校化学学报,1997,18(10):1585~1589
[40]黄玲,黄春辉,稀土配合物的光致发光和电致发光研究,化学学报,2000,58(12):1493~1498
[41]鲁桂,姚克敏,张肇英,镧系与直链系一组氨酸Schiff碱配合物合成、波谱与生物活性,应用化学,2001,I8(1):1~4.
[42]姚克敏,李宁,黄巧虹,Ln(III)-Cu(II)与直链醚-氨基酸新型Schiff碱异核配合物合成和催化,中国科学(B),1998,28(6):517
[43]李锦州,李刚,于文锦,呋喃甲酰基吡唑啉酮双席夫碱配合物的合成、表征及生物活性,中国稀土学报,2000,18(1):71
[44]杨正银,王流芳,2-羰基丙酸(吡啶-4-甲酰基)腙稀土双核配合物的合成、表征及抗肿瘤活性,应用化学1992,9(3),31~36
[45]陈德余,姚克敏,三种Gd3+直链醚席夫碱钆配合物EPR波谱研究,中国科学(B),1993,23(7):696
[46]易国斌,崔英德,陈德余,天冬酰胺Schiff碱稀土配合物的合成、表征与抗O2-性能,化学通报,2002,2:119-122
[47]Kiritsis V., Michaelides A., Skoulika S., The isfrared spectra of some dimenthyl sulfoxide complexes, Inorg. Chem., 1998, 37: 3407~3411
[48]Brouca-Cabarrecq C., Fernandes A., Costes J. P., Catalytic ionic hydrogenations of ketones using molybdenum and tungsten complexes, Inorg. Chim. Acta., 2002, 332: 54~60
[49]游效曾,孟庆金,韩万书,配位化学进展,北京:高等教育出版社,2000
[50]朱善威,袁方,杨敏,有机镓、铟芳酰腙配合物的制备与结构表征,无机化学学报,2002,18(12):1221~1225
[51]Chan S-C., Koh L-L., Leung P-H., Copper(II) complexes of the antitumour-related ligand salicylaldehyde acetylhydrazone (H2L) and the single-crystal X-ray structures of [{Cu(HL)H2O}2]·2(NO3) and [{Cu(HL) (pyridine) (NO3)}2], Inorg. Chim. Acta., 1995, 236(1/2): 101~108
[52]Tian Y-P, Duan C-Y, Zhao C-Y, Synthesis, Crystal Structure and Second-Order Optical Nonlinearity of Bis(2-chlorobenzaldehyde thiosemicarbazone)cadmium Halides (CdL2X2; X = Br, I), Inorg. Chem., 1997, 36: 1247-1252.
[53]唐波,张杰,王栩,新型主体试剂交联聚合β-环糊精-邻香草醛苯甲酰腙的合成及荧光法识别锌,分析化学,2002,30(10):1196~1200
[54]Lane, B.S., Burgess, K., Metal-catalyzed epoxidations of alkenes with hydrogen peroxide, Chemical Reviews, 103 (7): 2457~2473
[55]Zhou D, Yang N-L, Synthesis of narrow-polydispersity 3-star-polystyrene via nitroxide-mediated radical polymerization, American Chemical Society, Polymer Preprints, Division of Polymer Chemistry 40(2): 938~939
[56]Whittlesey M.K., Complexes containing metal-carbonσ-bonds of the groups iron, cobalt and nickel,including carbenes and carbines, J. Organomet. Chem., 2001, 29: 350~383
[57]蔣海军,异烟肼所致不良反应分析,中国药物应用与监测,2005,4:52~54
[58]Carcelli.M., Cozzint.P., Maccagin.T., Synthetic routes to mono-and bi-copper hydrazone complexes uncovered by computer simulation, Inorg. Chim. Acta., 2000, 303(2): 238~243
[59]Haskelberg L., Halogenation of aryloxyacetic acids and their homologs, J. Org. Chem., 1947, 12(1): 426~433
[60]Seiichi Y., 4-Mercapto-7-methylthio-2,1,3-benzoxadiazole for carboxylic acids, designed, Anal. Chem., 2001, 73(10): 2165~2171
[61]Srivatava K.N., Synthesis characterization and properties of Al Zn complexes with isonicotinoyl hydrazone, Inorg. Chim. Acta., 1986, 5: 85~90
[62]Rao T. R., Srivastava M. R., Synthesis and spectral studies of some lanthanide metal chelates of an unsymmetrical tridentate Schiff base, Synth. React. Inorg. Met-Org. Chem., 1992, 22(10): 1551~1564
[63]王明雄,邓汉芹,娄兆文,香草醛异烟酰腙与钴、镍、铜、锌和镉配合物的合成和性质研究,无机化学学报,1992,8(3):255~258
[64]Sekkina M.M. A., Synthesis characterization and properties of Mn Co Ni acetate complexes with isonicotinoyl hydrazone, J. Coord. Chem., 1984, 11: 83~90
[65]Teotia M.P., Synthesis, characterization and properties of Cr Mn Co complexes with isonicotinoyl hydrazone, Synth. React. Inorg. Met-Org. Chem., 1988, 18: 635~670
[66]邓汉芹,王明雄,杨桂春,胡椒醛缩异烟肼与钴、镍、铜和镉配合物的合成和表征,湖北大学学报(自然科学版),1991,13(1):66~72
[67]陈敬堂,廖代正,张若桦,具有铁磁偶合的新型双铜(II)和双钴(II)配合物,南开大学学报(自然科学版),1994,3:100~102
[68]陈敬堂,廖代正,张若桦,异烟肼缩β-二酮的双核铜(II)、钴(II)配合物的合成与磁性,南开大学学报(自然科学版),1992,1:6~11
[69]胡永钢,崔文平,陈营万,异烟肼铅(II)配合物的合成及结构研究,山西大学学报(自然科学版),1995,18(1):312~31
[70]徐丙阶,δ-阻滞剂治疗冲血性心力衰竭的机理与注意事项,江西医药, 1995,30(10):50
[71]张姝名,贾永金,王瑾玲,1-苯基-3-甲基-4-三氟乙酰基-5-吡唑啉酮缩水杨酰肼席夫碱的合成、表征及抑菌活性,天津师范大学学报(自然科学版), 2003,23(10):4~6
[72]Jiang Chongqiu, Tang Bo, Wang Chen, Analyst, 1996, 121(3): 317-320
[73]He Shuiyang, Cao Wenkai, Yang Rui, Crystal Structure and Biological Activity of Copper(II) Complex with Two Aqua and 2-oxo-propionic Acid Salicyloyl Hydrazone, Chinese Journal of Inorganic Chemistry , 2003, 19(7): 699-703
[74]何水样,陈云利,杨锐,武望婷,史启桢,王汝贤,水杨醛水杨酰腙及其稀土配合物的合成、波谱研究及生物活性,有机化学,2003,23(12):1387~1392
[75]WangJ.T., Liu F.Q., Zhang Y.W., Synthesis and structure of pentacoordinate tin(Ⅵ) complexes, J. Organomet. Chem., 1989, 375: 173~181
[76]杨频,生物化学中的稀土元素,化学通报,1985,7:31~35
[77]计亮年,黄锦汪,莫庭焕,生物无机化学导论,第二版,广州:中山大学出版社,2001
[78]杨锐,何水样,武望婷,[Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]2·phen·4H2O超分子化合物的晶体结构、荧光性质及热稳定性,高等学校化学学报,2005,26(3):401~406
[79]Steiner T., The hydrogen bond in the solid state, Angew. Chem. Int. Ed., 2002, 41: 48~76
[80]李蓉,异烟酰腙配体多孔配位聚合物的合成、结构与吸水-脱水性能研究,硕士学位论文,天津大学,2007
[81]张华,现代有机波谱分析,北京:化学工业出版社,2005
[82]龚筱群,陈洪超,水杨酰肼的合成工艺研究,华西医学杂志,1997,12(4):240~242