聚吡唑硼酸盐钒氧配合物的合成及对苯酚红催化溴化活性

doi:10.11944/j.issn.1000-0518.2016.11.160033

摘要/Abstract

摘要：

在室温溶液反应中设计合成了一个新的三聚-4碘代吡唑硼酸的钒氧配合物:[VO(C₆H₉O₂)(Tp^4I)]·2H₂O(Tp^4I=三聚-4-碘代吡唑硼酸盐)。通过元素分析、红外光谱、紫外光谱、热重、X射线粉末和单晶衍射等技术手段对其结构进行了表征。以苯酚红为底物,在过氧化氢的存在下,进行仿生催化溴化的研究。结构分析表明,中心金属钒为6配位,与配位原子形成了一个八面体几何构型。配体三聚4-碘吡唑硼酸盐(Tp^4I)采取三齿螯合配位模式。在仿生催化溴化实验中,配合物对苯酚红的溴化氧化反应表现出良好的催化活性,催化该反应体系的反应速率常数达到k=2.826×10² (mol/L)^-2·s^-1。同时将此反应体系应用于过氧化氢的检测。

关键词: 钒氧配合物, 三聚-4碘代吡唑硼酸盐, 晶体结构, 仿生催化溴化

Abstract:

Oxovanadium complex [VO(C₆H₉O₂)(Tp^4I)]·2H₂O(Tp^4I=tri-(4-lodopyrazole)borate) was designed and synthesized. The spectral and structural characters of the complex were analyzed by elemental analysis, IR spectroscopy, UV spectroscopy, thermogravimetric analysis, X-ray powder diffraction and single crystal X-ray diffraction analysis. The structural analysis shows that the complex has an octahedron geometry with hexa-coordinated metal. Ligand tri-(4-lodopyrazole)borate adopts a tridentate chelating coordination mode. The complex exhibits good catalytic activity in the mimic bromination of phenol red, and the reaction rate constant is 2.424×10² (mol/L)^-2·s^-1. Meanwhile, the reaction system was applied in the hydrogen peroxide determination.

Key words: oxovanadium complex, tri-(4-lodopyrazole)borate, crystal structure, mmimic catalytic bromination

冯晓东, 林晓濛, 王杨, 白凤英, 邢永恒. 聚吡唑硼酸盐钒氧配合物的合成及对苯酚红催化溴化活性[J]. 应用化学, 2016, 33(11): 1303-1309.

FENG Xiaodong, LIN Xiaomen, WANG Yang, BAI Fengying, XING Yongheng. Synthesis and Phenol Red Catalytic Bromination Activity of Polypyrazole Borate Oxovanadium Complex[J]. Chinese Journal of Applied Chemistry, 2016, 33(11): 1303-1309.

参考文献

[1]	Crans D C,Smee J J,Gaidamauskas E,et al.The Chemistry and Biochemistry of Vanadium and the Biological Activities Exerted by Vanadium Compounds[J]. Chem Rev,2004,104(2):849-902.
[2]	Rehder D.The Bioinorganic Chemistry of Vanadium[J]. Angew Chem Int Ed,1991,30(2):148-167.
[3]	Zhu J,Cao L,Wu Y,et al.Building 3D Structures of Vanadium Pentoxide Nanosheets and Application as Electrodes in Supercapacitors[J]. Nano Lett,2013,13(11):5408-5413.
[4]	Muster J,Kim G T,Krsti? V,et al. Electrical Transport Through Individual Vanadium Pentoxide Nanowires[J]. Adv Mater,2000,12(6):420-424.
[5]	La Barre S,Potin P,Leblanc C,et al.The Halogenated Metabolism of Brown Algae(Phaeophyta), Its Biological Importance and Its Environmental Significance[J]. Mar Drugs,2010,8(4):988-1010.
[6]	Butler A,Carter-Franklin J N. The Role of Vanadium Bromoperoxidase in the Biosynthesis of Halogenated Marine Natural Products[J]. Nat Prod Rep,2004,21(1):180-188.
[7]	Winter J M,Moore B S.Exploring the Chemistry and Biology of Vanadium-Dependent Haloperoxidases[J]. J Biol Chem,2009,284(28):18577-18581.
[8]	Butler A.Mechanistic Considerations of the Vanadium Haloperoxidases[J]. Coord Chem Rev,1999,187(1):17-35.
[9]	Almeida M,Filipe S,Humanes M,et al.Vanadium Haloperoxidases from Brown Algae of the Laminariaceae Family[J]. Phytochemistry,2001,57(5):633-642.
[10]	Natalio F,André R,Hartog A F,et al.Vanadium Pentoxide Nanoparticles Mimic Vanadium Haloperoxidases and Thwart Biofilm Formation[J]. Nat Nanotechnol,2012,7(8):530-535.
[11]	De Boer E,Tromp M G M,Plat H,et al. Vanadium(Ⅴ) as an Essential Element for Haloperoxidase Activity in Marine Brown Algae:Purification and Characterization of a Vanadium(Ⅴ)-Containing Bromoperoxidase from Laminaria Saccharina[J]. Biochim Biophys Acta,1986,872(1):104-115.
[12]	Littlechild J,Rodriguez E G,Isupov M.Vanadium Containing Bromoperoxidase Insights into the Enzymatic Mechanism Using X-ray Crystallography[J] J Inorg Biochem,2009,103:617-621.
[13]	Feng X D,Zhang R,Wang X Y,et al.Mimicing Bromoperoxidase Bromoperoxidase for Copper Complexes:Synthesis, Structures and Properties of Cu(Ⅱ) Triazine Pyrazolyl Complex[J]. Polyhedron,2015,90:69-76.
[14]	Chen C,Sun Q,Ren D X,et al.Bromoperoxidase Mimic as Catalysts for Oxidative Bromination-Synthesis, Structures and Properties of the Diversified Oxidation State of Vanadium(Ⅲ, Ⅳ and Ⅴ) Complexes with Pincer N-heterocycle Ligands[J]. CrystEngComm,2013,15(27):5561-5573.
[15]	Feng X D,Zhang X X,Wang Z N,et al.Mimicking Vanadium Haloperoxidases: Vanadium(Ⅲ) Carboxylic Acid Complexes and Their Application in H2O2 Detection[J]. New J Chem,2016,40:1222-1229
[16]	Ren D X,Cao Y Z,Chen C,et al.Vanadium Haloperoxidases Model Compounds: Synthesis, Structural Characterization and Mimic Catalytic Bromination Activity of [VO(C2O4)(2,2'-bipy)(H2O)]·C2H5OH and VO(C2O4)(phen)(H2O)[J]. Chem Res Chinese Univ,2012,28(5):768-774.
[17]	Zhang R,Liu J,Chen C,et al.Synthesis, Structures and Properties of the Catalytic Bromination Reaction of a Series of Novel Scorperate Oxidovanadium Complexes with the Potential Detection of Hydrogen Peroxide in Water[J]. Spectrochim Acta,Part A,2013,115(11):476-482.
[18]	Trofimenko S.Boron-pyrazole Chemistry[J]. J Am Chem Soc,1966,88(8):1842-1844.
[19]	Trofimenko S.Boron-pyrazole Chemistry.Ⅱ.Poly(1-pyrazolyl)-borates[J]. J Am Chem Soc,1967,89(13):3170-3177.
[20]	Sheldrick G M.Program for Crystal Structure Refinement[M]. University of Göttingen:Göttingen,Göermany,1997.
[21]	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.