多元钒氧化合物的合成、结构和理化表征
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摘要
钒化合物具有丰富的生理学活性,在含钒生物酶和模拟胰岛素样功能方面受到了重视。合成新型含钒化合物对了解钒的配位化学性质和开发具有胰岛素功能的抗糖尿病的无机药物具有非常重要的理论意义。本论文的工作如下:
1、以VO(acac)_2为起始物,以phen或2,2’-bipy为刚性支撑配体,有机羧酸为第三配体,合成了相应的四元钒氧配合物VO(acac)LL’(L = Phen, L’= Fta (1), SMIA (2), MNBA (3); L = 2,2’-bipy, L’= MBBA(4))。X-射线晶体衍射结果表明,其组成是四元单核钒(IV)结构,中心钒原子均为VO_4N_2的八面体构型。对化合物进行了IR、CV和EPR的表征,并对合成体系的各种影响因素进行了讨论。在该体系中,当使用氨基酸做为第三配体时,到了无羧酸配位的产物类型,六核钒化合物[(phen)_4V_6O_(12)(MeOH)_4]·MOH·H_2O (5)和单核双氧钒化合物VO_2(acac)(phen) (6)。
2、以VO(acac)_2为起始物,以dibim刚性支撑配体,以草酸为第三配体,合成了三元羧酸配合物VO(OX)(dibim).MeOH (7)。X-射线晶体衍射结果表明,其组成是三元单核钒(IV)结构,中心钒原子均为VO_3N_3的八面体构型。对该化合物进行了IR和EPR表征。
3、以水杨醛和二氨基硫脲形成的希夫碱Btc为配体,意外得到一个配体环化后的钒氧化合物VO(cyclic-Btc)(EtOH)_2 (8)。X-射线晶体衍射结果表明,化合物8中含有一个噻唑环,中心钒原子均为VO_4N_2的八面体构型。它的EPR谱磁性曲线表明该化合物中存在V(IV)离子。
With the discovery of vanadium haloperoxidases and nitrogenase, much more interests have been concentrated on the coordination and the bioinorganic characteristics of vanadium compouds. Many oxovanadium (IV) complexes have the potential insulin-mimetic effects and have been reganded as the one kind of inorganic drug to cure diabetes. The studies of the vanadium coordination and bioinorganic chemistry have developed extensively in recent years. The following are the study results in this work.
1. Four novel quaternary vanadium complexes with carboxylic acid, acac and phen or 2,2’-bipy, VO(acac)LL’(L = Phen, L’= Fta (1), SMIA (2), MNBA (3); L = 2,2’-bipy, L’= MBBA(4) were synthesized and characterized by single crystal X-ray diffraction. The central vanadyl ion is in a distorted octahedral VO4N2 environment. The complexes were characterized by IR, CV and EPR spectroscopy, and the factors affecting the synthesis of the quaternary complexes were also discussed. Hexanuclear- and dioxo- vanadium compounds, [(phen)4V6O12(MeOH)4]·MOH·H2O (5) and VO2(acac)(phen) (6),were isolated from the reaction system with the addition of animo acid ligands.
2. One oxovanadium (IV) compound [VO(OX)(dibim)].CH3OH (7) was synthesized by the reaction of VO(acac)2, OX and dibim ligands, and characterized by X-ray crystallography, IR and EPR.
3. One unexpected vanadium compounds VO(Cyclic-Btc)(EtOH)2 (8) was obtained from the reaction system of VO(acac)2 and Btc ligand in ethanol, where Cyclic-Btc was resulted from the cyclization of Btc in the synthesis process. X-ray crystallography revealed that complex 8 contains a thiadiazole ring and X-band EPR spectroscopy of the sample indicated the existence of vanadium (IV) ions in the compound.
1、以VO(acac)_2为起始物,以phen或2,2’-bipy为刚性支撑配体,有机羧酸为第三配体,合成了相应的四元钒氧配合物VO(acac)LL’(L = Phen, L’= Fta (1), SMIA (2), MNBA (3); L = 2,2’-bipy, L’= MBBA(4))。X-射线晶体衍射结果表明,其组成是四元单核钒(IV)结构,中心钒原子均为VO_4N_2的八面体构型。对化合物进行了IR、CV和EPR的表征,并对合成体系的各种影响因素进行了讨论。在该体系中,当使用氨基酸做为第三配体时,到了无羧酸配位的产物类型,六核钒化合物[(phen)_4V_6O_(12)(MeOH)_4]·MOH·H_2O (5)和单核双氧钒化合物VO_2(acac)(phen) (6)。
2、以VO(acac)_2为起始物,以dibim刚性支撑配体,以草酸为第三配体,合成了三元羧酸配合物VO(OX)(dibim).MeOH (7)。X-射线晶体衍射结果表明,其组成是三元单核钒(IV)结构,中心钒原子均为VO_3N_3的八面体构型。对该化合物进行了IR和EPR表征。
3、以水杨醛和二氨基硫脲形成的希夫碱Btc为配体,意外得到一个配体环化后的钒氧化合物VO(cyclic-Btc)(EtOH)_2 (8)。X-射线晶体衍射结果表明,化合物8中含有一个噻唑环,中心钒原子均为VO_4N_2的八面体构型。它的EPR谱磁性曲线表明该化合物中存在V(IV)离子。
With the discovery of vanadium haloperoxidases and nitrogenase, much more interests have been concentrated on the coordination and the bioinorganic characteristics of vanadium compouds. Many oxovanadium (IV) complexes have the potential insulin-mimetic effects and have been reganded as the one kind of inorganic drug to cure diabetes. The studies of the vanadium coordination and bioinorganic chemistry have developed extensively in recent years. The following are the study results in this work.
1. Four novel quaternary vanadium complexes with carboxylic acid, acac and phen or 2,2’-bipy, VO(acac)LL’(L = Phen, L’= Fta (1), SMIA (2), MNBA (3); L = 2,2’-bipy, L’= MBBA(4) were synthesized and characterized by single crystal X-ray diffraction. The central vanadyl ion is in a distorted octahedral VO4N2 environment. The complexes were characterized by IR, CV and EPR spectroscopy, and the factors affecting the synthesis of the quaternary complexes were also discussed. Hexanuclear- and dioxo- vanadium compounds, [(phen)4V6O12(MeOH)4]·MOH·H2O (5) and VO2(acac)(phen) (6),were isolated from the reaction system with the addition of animo acid ligands.
2. One oxovanadium (IV) compound [VO(OX)(dibim)].CH3OH (7) was synthesized by the reaction of VO(acac)2, OX and dibim ligands, and characterized by X-ray crystallography, IR and EPR.
3. One unexpected vanadium compounds VO(Cyclic-Btc)(EtOH)2 (8) was obtained from the reaction system of VO(acac)2 and Btc ligand in ethanol, where Cyclic-Btc was resulted from the cyclization of Btc in the synthesis process. X-ray crystallography revealed that complex 8 contains a thiadiazole ring and X-band EPR spectroscopy of the sample indicated the existence of vanadium (IV) ions in the compound.
引文
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[35]. R.E. Drew, F.W.B. Einstein, Inorg. Chem., 1972, 11, 1079.
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[41]. M.A.K. Ahmed, H. Fiellvag, A. Kjekshus, et al., Z. Anorg. Allg. Chem. 2004, 630, 2311.
[42]. T.S. Smith, C.A. Root, J.W. Kampf, et.al., J. Am. Chem. Soc. 2000, 122, 767.
[43]. B.K. Koo, Y.J. Jang, U. Lee, Bull. Korean Chem. Soc. 2003, 24, 1014.
[44]. Y.J. Qi, Y.L. Yang, M.H. Cao, et al., J. Mol. Struct., 2003, 648, 191.
[45]. E.J. Tolis, M.J. Manos, A.J. Tasiopoulos, et al., Angew. Chem. Inter. Edit., 2002, 41, 2797.
[46]. Y. Dong, R.K. Narla, E. Sudbeck, et al. J. Inorg. Biochem., 2000, 78, 321.
[47]. K. Isobe, S.N. Ooi, K. Yukio, et al., Chem. Lett., 1975, 35.
[48]. H.Y. Xing, K. Aoki, F.Y. Bai, Synth. React. Inorg. Met-org. Chem., 2003, 33, 1801.
[49]. Y.L. Fu, N. Lin, W. Seik, Act. Crystallogr. Sect E, 2004, 60 m1584.
[50]. J. Tatiersky, P. Schwendt, J. Marek, New J. Chem., 2004, 28, 127.
[51]. S.J. Kayitha, K. L. Panchanatheswanran, N. John, Acta Crystallogr. Sect E, 2006, 62, m529.
[1]. G.M. Sheldrick, SHELXS-97, SHELXL-97, Programs for Crystal Structure Analysis, University of G?ttingen, Germany 1997.
[2]. K. Brandenburg, DIAMOND. Visual Crystal Structure Information System.Version 3.1. Crystal Impact, Bonn, Germany 2005.
[1]. L.F. Vilas, J. Boas, P. Costa, in Comprehensive Coordination Chemistry, ed G. Wilkinson, R.D. Gillard, J.A. McCleverty, Pergamon, Oxford, 1987, 3, 453.
[2]. C. Holloway, M. Melnik, Rev. Inorg. Chem., 1985, 7, 75.
[3]. R. Tawa, K. Uchida, J. Taniyama, et al., Pharmacol., 1999, 51, 119.
[4]. H.J. Yue, D. Zhang, Z. Shi, et al., Inorg. Chem. Commun., 2006, 9, 959
[1]. K. Nakamoto, Infrared and Raman Spectra of Inorganic Compounds, 5th ed.,1997, p. 271
[2]. N.D. Chasteen, in: L.J. Berliner, J. Reuben (Eds.), Biological Magnetic Resonance, vol. 3, Plenum Press, New York, 1981, p. 53.
[3]. S.W. Taylor, B. Kammerer, E. Bayer, Chem. Rev., 1997, 97, 333.
[4]. T.S. Smith, C.A. Root, J.W. Kampf, et al., J. Am.Chem. Soc., 2000, 122, 767.
[5]. C.R. Cornman, E.P. Zovinka, Y.D. Boyajian,et al., Inorg. Chem., 1995, 34, 4213.
[6]. A.J. Tasiopoulos, A.N. Troganis, A. Evangelou,et al., Chem. Eur. J., 1999, 5, 910.
[7]. A.L.P. Houseman, R. LoBrutto, W.D. Frasch, Biochemistry, 1995, 34, 3277
[8]. B.H. Hamstra, A.L.P. Houseman, G.J. Colpas, et al., Inorg. Chem., 1997, 36, 4866
[9]. ?. Ucar, A. Bulut, A. Karadag, et al. J. Mol. Struct., 2007, 837, 38.
[1]. S.S. Amin, K. Cryer, B. Zhang, et al, Inorg. Chem., 2000, 39, 406.
[2]. E.J. Manos, A.J. Tasiopoulos, E.J. et al., Chem. Eur. J. 2003, 9, 695.
[3]. Y. Gong, C.W. Hu, H. Li, Journal of Molecular Structure 2005, 749, 31.
[4]. K. Isobe, S.N. Ooi, K. Yukio, et al., Chem. Lett., 1975, 35.
[5]. Y.L. Fu, N. Lin, W. Seik, Act. Crystallogr. Sect E, 2004, 60 m1584.
[2]. J.O. Nriagu, in Vanadium in the Environment, Part One: Chemistry and Biochemisty,Nriagu, J.O., Ed., John Wiley & Sons, New York, 1998, Chapter 1.
[3]. D.R. Lide, Handbook of Chemistry and Physics, Ed.,72nd Edition, 1991-1992
[4]. N.D.Chasteenetal.Thebiochemistryofvanadium.StructureandBonding.1993,105
[5]. Comprehensive Coordination Chemistry, Wilkinson, G., Ed.; Pergamon Press, Oxford,1987, 3, 454.
[6]. A. Butler, C.J. Carrano, Coord. Chem. Rev. 1991, 109, 61.
[7]. Vanadium in Biological Systems: Physiology and Biochemistry, Chasteen, N.D., d.; KluwerAcademic Publishers, Dordrecht, 1990.
[8]. D.C. Crans, S.S. Amin, A.D. Keramidas, in Vanadium in the Environment, Part One:Chemistry and Biochemisty, Nriagu, J.O., Ed.; John Wiley & Sons, New York, 1998,Chapter 4
[9]. E.M. Page, Coord. Chem. Rev. 1998, 172, 111
[10]. K. kustin, I.G. Macara, Comments Inorganic Chemistry, 1982, 2, 1.
[11]. T.D. Tullius, W.O. Gillum, J. Am. Chem. Soc. 1980,102
[12]. N.D. Chasteen, Struct.Bonding()Berline, 1983, 53, 105.
[13]. D.W. Boyd., K. Kustin, Adv. Inorg. Biochem, 1984, 6, 2312
[14]. A. Butler, M.J. Danztiz, H. Eekert, J.Am.Chem.Soc., 1987, 109, 1864.
[15]. R. Wever, E. DeBobsom, H. Platand, et al., FEBS Lett.,1987, 1, 216.
[16]. H. Vilter, Phytochemistry, 1984, 23, 1387.
[17].杨晓改,杨晓达,王燮,化学进展,2002, 14, 279.
[18]. D. Rehder, Angew. Chem. Int. Ed., 1991, 30, 148.
[19]. B. Zhang, S. Zhang, B.Chen, Biometals, 1997, 10, 291.
[20]. H. Sigel, A. Sigel. in Metal Ions in Biological Systems, New York: Marcel Dekker Inc., 1995, vol 31.
[21]. I.G. Fantus, E. Tsiani, Mol. Cell Biochem., 1998, 182, 109.
[22]. Y. Shechter, I. Goldwaser, M. Mironchik, et al. Coord. Chem. Rev., 2003, 237, 3.
[23]. Y. Schechter, S. Karlish, Nature, 1980, 284, 556.
[24]. C.E. Heyliger, Science, 1985, 227, 1474.
[25].屈健,中国饲料,1997, 15 21.
[26].杨频,韩广业,化学通报,2001, 9, 553
[27].曾福礼,赵青,王欣,等..兰州大学学报(自然科学版),1997, 33, 85.
[28]. H. Watanabe, M. Nakai, K. Komazawa, et al., Med Chem, 1994, 29, 876.
[29].谢明进,刘伟平,李玲,等,化学学报,2002, 60, 892.
[30]. H. Sakurai, Z. Taira, N. Sakai, Inorg. Chim. Acta., 1988, 151, 85.
[31]. A. Shaver, J.B. Ng, R.C. Hynes, et al., Acta Crystallogr., 1994, C50, 1044
[32]. A. Shaver, D.A. Hall, et al., Inorg Chem, 1993, 323, 109.
[33]. V. Nikola, C. Djprdjevic, J C S Dalton Trans, 1973, 1137
[34]. D. Begin, F.W.B. Einstein, J. Field, Inorg. Chem., 1975, 14, 1785.
[35]. R.E. Drew, F.W.B. Einstein, Inorg. Chem., 1972, 11, 1079.
[36].周兴旺,陈中,陈清西,等,生物化学与生物物理学报,2000, 32, 133.
[37]. B.I. Ponser, R. Faure, J.W. Burgess, et al., J. Biol. Chem., 1994, 269, 4596.
[38]. A.P. Bevan, J.W. Burgess, J.F. Yale, et al., Am. J. Physiol.,1995, 268, E60.
[39].邵美成,王丽峰,张泽莹,化学学报,1983, 985.
[40]. A.L. Filgueiras, A. Horn, R.A. Howie, et al., Acta Crystallogr. Sect E, 2001, 57, m157.
[41]. M.A.K. Ahmed, H. Fiellvag, A. Kjekshus, et al., Z. Anorg. Allg. Chem. 2004, 630, 2311.
[42]. T.S. Smith, C.A. Root, J.W. Kampf, et.al., J. Am. Chem. Soc. 2000, 122, 767.
[43]. B.K. Koo, Y.J. Jang, U. Lee, Bull. Korean Chem. Soc. 2003, 24, 1014.
[44]. Y.J. Qi, Y.L. Yang, M.H. Cao, et al., J. Mol. Struct., 2003, 648, 191.
[45]. E.J. Tolis, M.J. Manos, A.J. Tasiopoulos, et al., Angew. Chem. Inter. Edit., 2002, 41, 2797.
[46]. Y. Dong, R.K. Narla, E. Sudbeck, et al. J. Inorg. Biochem., 2000, 78, 321.
[47]. K. Isobe, S.N. Ooi, K. Yukio, et al., Chem. Lett., 1975, 35.
[48]. H.Y. Xing, K. Aoki, F.Y. Bai, Synth. React. Inorg. Met-org. Chem., 2003, 33, 1801.
[49]. Y.L. Fu, N. Lin, W. Seik, Act. Crystallogr. Sect E, 2004, 60 m1584.
[50]. J. Tatiersky, P. Schwendt, J. Marek, New J. Chem., 2004, 28, 127.
[51]. S.J. Kayitha, K. L. Panchanatheswanran, N. John, Acta Crystallogr. Sect E, 2006, 62, m529.
[1]. G.M. Sheldrick, SHELXS-97, SHELXL-97, Programs for Crystal Structure Analysis, University of G?ttingen, Germany 1997.
[2]. K. Brandenburg, DIAMOND. Visual Crystal Structure Information System.Version 3.1. Crystal Impact, Bonn, Germany 2005.
[1]. L.F. Vilas, J. Boas, P. Costa, in Comprehensive Coordination Chemistry, ed G. Wilkinson, R.D. Gillard, J.A. McCleverty, Pergamon, Oxford, 1987, 3, 453.
[2]. C. Holloway, M. Melnik, Rev. Inorg. Chem., 1985, 7, 75.
[3]. R. Tawa, K. Uchida, J. Taniyama, et al., Pharmacol., 1999, 51, 119.
[4]. H.J. Yue, D. Zhang, Z. Shi, et al., Inorg. Chem. Commun., 2006, 9, 959
[1]. K. Nakamoto, Infrared and Raman Spectra of Inorganic Compounds, 5th ed.,1997, p. 271
[2]. N.D. Chasteen, in: L.J. Berliner, J. Reuben (Eds.), Biological Magnetic Resonance, vol. 3, Plenum Press, New York, 1981, p. 53.
[3]. S.W. Taylor, B. Kammerer, E. Bayer, Chem. Rev., 1997, 97, 333.
[4]. T.S. Smith, C.A. Root, J.W. Kampf, et al., J. Am.Chem. Soc., 2000, 122, 767.
[5]. C.R. Cornman, E.P. Zovinka, Y.D. Boyajian,et al., Inorg. Chem., 1995, 34, 4213.
[6]. A.J. Tasiopoulos, A.N. Troganis, A. Evangelou,et al., Chem. Eur. J., 1999, 5, 910.
[7]. A.L.P. Houseman, R. LoBrutto, W.D. Frasch, Biochemistry, 1995, 34, 3277
[8]. B.H. Hamstra, A.L.P. Houseman, G.J. Colpas, et al., Inorg. Chem., 1997, 36, 4866
[9]. ?. Ucar, A. Bulut, A. Karadag, et al. J. Mol. Struct., 2007, 837, 38.
[1]. S.S. Amin, K. Cryer, B. Zhang, et al, Inorg. Chem., 2000, 39, 406.
[2]. E.J. Manos, A.J. Tasiopoulos, E.J. et al., Chem. Eur. J. 2003, 9, 695.
[3]. Y. Gong, C.W. Hu, H. Li, Journal of Molecular Structure 2005, 749, 31.
[4]. K. Isobe, S.N. Ooi, K. Yukio, et al., Chem. Lett., 1975, 35.
[5]. Y.L. Fu, N. Lin, W. Seik, Act. Crystallogr. Sect E, 2004, 60 m1584.