过氧钒配合物的合成、结构及模拟过氧化酶催化溴化动力学

doi:10.3724/SP.J.1095.2013.20546

摘要/Abstract

摘要： 根据模拟钒卤代过氧化物酶(V-HPOs)活性中心的配位环境，设计并合成了2种新型过氧钒配合物：Na[VO(O2)2(C10H8N2)]·8H2O(1)和K3H[(VO)2(O2)4(μ2-O)]·H2O(2)，通过元素分析、红外光谱和紫外光谱对其进行了表征，并通过X射线单晶衍射方法确定了其结构。配合物1晶体属于三斜晶系，空间群：P-1，a=0.7213(2) nm,b=1.1269(4) nm,c=1.3728(4) nm,α=68.349(4)°,β=89.178(4)°,γ=88.050(4)°,V=1.0365(6) nm3。配合物2的晶体属于单斜晶系，空间群：P21/c,a=0.67047(12) nm,b=0.99503(18) nm,c=1.5817(3) nm,α=γ=90°,β=93.739(2)°,V=1.0530(3) nm3。配合物1和2分别是五角双锥和八面体配位构型。通过催化溴化反应活性研究发现，2种配合物均可作为潜在的钒卤代过氧化物酶模拟物。

关键词: 钒卤代过氧化物酶, 钒过氧配合物, 晶体结构, 催化活性

Abstract: Based on mimicking the environment of the active center of vanadium haloperoxidase(V-HPOs), we designed and synthesized two kinds of peroxovanadium complexes:Na[VO(O2)2(C10H8N2)]·8H2O(1) and K3H[(VO)2(O2)4(μ2-O)]·H2O(2), which were structurally characterized by X-ray single crystal diffraction, elemental analysis, IR and UV-Vis spectroscopies. Structural analyses reveal that complex 1 crystallized in an triclinic system with space group P-1, a=0.7213(2) nm, b=1.1269(4) nm, c=1.3728(4) nm, α=68.349(4)°, β=89.178(4) °, γ=88.050(4)°, V=1.0365(6) nm3 and the complex 2 crystallized in an monoclinic system with space group P21/c, a=0.67047(12) nm, b=0.99503(18) nm, c=1.5817(3) nm, α=γ=90°, β=93.739(2)°, V=1.0530(3) nm3. Complex 1 has a distorted pentagonal bipyramidal geometry, while complex 2 has a distorted octahedron geometry. In addition, by studying the bromination reaction activity, it shows that the peroxovanadium complexes can be considered as a potential functional model of bromoperoxidase.

Key words: vanadium haloperoxidase, peroxovanadium complex, crystal structure, catalytic activity

中图分类号:

O614

陈晨, 张瑞, 王璇, 曹运珠, 白凤英, 张晓溪, 李光华, 施展, 邢永恒. 过氧钒配合物的合成、结构及模拟过氧化酶催化溴化动力学[J]. 应用化学, DOI: 10.3724/SP.J.1095.2013.20546.

CHEN Chen2, ZHANG Rui2, WANG Xuan2, CAO Yunzhu2, BAI Fengying1*, ZHANG Xiaoxi2, LI Guanghua3, SHI Zhan3, XING Yongheng2. Synthesis, Structure and Mimic Haloperoxidase Catalytic Activity of Peroxovanadium Complexes[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2013.20546.

参考文献

[1] Lodyga-Chruscinska E,Micera G,Garribba E. Complex Formation in Aqueous Solution and in the Solid State of the Potent Insulin-Enhancing VⅣO2+ Compounds Formed by Picolinate and Quinolinate Derivatives[J]. Inorg Chem,2011,50(3):883-899.

[2] Wikete C,Wu P,Zampella G,et al. Glycine- and Sarcosine-Based Models of Vanadate-Dependent Haloperoxidases in Sulfoxygenation Reactions[J]. Inorg Chem,2007,46(1):196-207.

[3] Plass W. Chiral and Supramolecular Model Complexes for Vanadium Haloperoxidases:Host-Guest Systems and Hydrogen Bonding Relays for Vanadate Species[J]. Coord Chem Rev,2011,255(19/20):2378-2387.

[4] Plass W. Supramolecular Interactions of Vanadate Species:Vanadium(Ⅴ) Complexes with N-Salicylidenehydrazides as Versatile Models[J]. Coord Chem Rev,2003,237(1/2):205-212.

[5] Marchetti F,Pettinari C,Nicola C D,et al. Synthesis and Characterization of Novel Oxovanadium(Ⅳ) Complexes with 4-Acyl-pyrazolone Donor Ligands:Evaluation of Their Catalytic Activity for the Oxidation of Styrene Derivatives[J]. Appl Catal,2010,378(2):211-220.

[6] Rehder D. The Coordination Chemistry of Vanadium as Related to Its Biological Functions[J]. Coord Chem Rev,1999,182(1):297-322.

[7] Pohlmann A,Nica S,Luong T K K,et al. Dioxovandium(Ⅴ) Complexes with Side Chain Substituted N-Salicylidenehydrazides Modelling Supramolecular Interactions in Vanadium Haloperoxidases[J]. Inorg Chem Commun,2005,8:289-292.

[8] Messerschmidt A,Prsde L,Wever R. Implications for the Catalytic Mechanism of the Vanadium-Containing Enzyme Chloroperoxidase from the Fungus Curvularia Inaequalis by X-Ray Structures of the Native and Peroxide Form[J]. Biol Chem,1997,378(3/4):309-315.

[9] Winter G E M,Butler A. Inactivation of Vanadium Bromoperoxidase: Formation of 2-Oxohistidine[J]. Biochemistry,1996,35(36):11805-11811.

[10] Rehder D. Bioinorganic Vanadium Chemistry[M]. Hamburg,John Wiley & Sons,Germany,2008.

[11] Xing Y H,Aoki K,Bai F Y,et al. Synthesis and Structure of Di-u-oxo-bistripyrazolylborato Dioxo Vanadium(Ⅴ) Complex with Lattice of Diacetonitrile[J]. J Chem Crystallogr,2008,38:327-331.

[12] Romanowski G,Wera M. Mononuclear and Dinuclear Chiral Vanadium(Ⅴ) Complexes with Tridentate Schiff Bases Derived form R(-)-1,2-diaminopropane:Synthesis, Structure, Characterization and Catalytic Properties[J]. Polyhedron,2010,29(13):2747-2754.

[13] Ligtenbarg A G J,Hage R,Feringa B L. Catalytic Oxidations by Vanadium Complexes[J]. Coord Chem Rev,2003,237(1/2):89-101.

[14] Santoni G,Rehder D. Structural Models for the Reduced Form of Vanadate-dependent Peroxidases:Vanadyl Complexes with Bidentate Chiral Schiff Base Ligand[J]. J Inorg Biochem,2004,98(5):758-764.

[15] Rehder D. Biological and Medicinal Aspects of Vanadium[J]. Inorg Chem Commun,2003,6(5):604-617.

[16] Maurya M R,Khan A A,Azam A,et al. Vanadium Complexes Having [VⅣO]2+ and [VVO2]+ Cores with Binucleating Dibasic Tetradentate Ligands:Synthesis, Characterization, Catalytic and Antiamoebic Activities[J]. J C C Dalton Trans,2010,39(5):1345-1360.

[17] Colpas G J,Hamstra B J,Kampf J W,et al. Functional Models for Vanadium Haloperoxidase:Reactivity and Mechanism of Halide Oxidation[J]. J Am Chem Soc,1996,118(14):3469-3478.

[18] Conte V,Coletti A,Floris B,et al. Mechanistic Aspects of Vanadium Catalysed Oxidations with Peroxides[J]. Coord Chem Rev,2011,255(19/20):2165-2177.

[19] Sheldrick G M. SADABS,Program for Area Detector Adsorption Correction[M]. Institute for Inorganic Chemistry, University of Gttingen:Gttingen,Germany,1996.

[20] Sheldrick G M. SHELX-97,Program for Crystal Structure Analysis[M]. University of Gottingen:Gottingen,Germany,1997.

[21] LI Zhangpeng,XING Yongheng,ZHANG Yuanhong,et al. Synthesis, Structure and Quantum Chemistry Calculation of Scorpionate Oxovanadium Complexes with Benzoate[J]. Acta Phys Chim Sin,2009,25:741-746(in Chinese).

李章朋,刑永恒,张元红,等. 蝎型钒氧苯甲酸配合物的合成、结构及量化计算[J]. 物理化学学报,2009,25:741-746.

[22] Sarmah S,Kalita D,Hazarika P,et al. Synthesis of New Dinuclear and Mononuclear Peroxovanadium(Ⅴ) Complexes Containing Biogenic Co-ligands:A Comparative Study of Some of Their Properties[J]. Polyhedron,2004,23(7):1097-1107.

[23] Reis P M,Silva J A L,Silva J J R F D,et al. Amavadine as a Catalyst for the Peroxidative Haloperoxidative Halogenation, Hydroxylation and Oxygenation of Alkanes and Benzene[J]. Chem Commun,2000,19:1845-1846.

[24] Conte V,Bortolini O,Carraro M,et al. Models for the Active Site of Vanadium-dependent Haloperoxidases:Insight into the Solution Structure of Peroxo Vanadium Compounds[J]. J Inrog Biochem,2000,80(1/2):41-49.

[25] Zampella G,Kravitz J Y,Webster C E,et al. Quantum Mechanical Models of the Resting State of the Vanadium-Dependent Haloperoxidase[J]. Inorg Chem,2004,43(14):4127-4136.

[26] Mandal T N,Roy S,Barik A K,et al. Synthesis and Structural Characterization of Copper(Ⅱ) and Vanadium(Ⅴ) Complexes of Pyridyl/pyrimidyl-pyrazole Derived Schiff Base Ligands-Metal Specific Adjustment of Ligand Binding Mode[J]. Polyhedron,2008,27(15):3267-3274.

[27] Chen C,Bai F Y,Xing Y H,et al. Synthesis, Structure and Mimicking Catalytic Bromination of Supramolecular Oxovanadium Complexes Containing Oxalate Ligand[J]. J Coord Chem,2013,66(4):671-688.

[28] Khan M I,Chang Y D,Chen Q,et al. Synthesis and Characterization of Binuclear Oxo-vanadium Complexes of Carbon Oxoanion Ligands. Crystal Structures of the Binuclear Vanadium(Ⅳ) Complex (NH4)[V2O2(OH)(C4O4)2(H2O)3]·H2O, of the Mixed-Valence Vanadium(Ⅴ)/Vanadium(Ⅳ)-Squarate Species [(n-C4H9)4N]4[V4O6(C4O4)5(H2O)4]·6H2O, and of the Binuclear Vanadium(Ⅳ)-Oxalate Species [V2O2Cl2(C2O4)(CH3Oh)4]·2Ph4Cl[J]. Inorg Chem,1994,33(26):6340-6350.