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在室温条件下,用相同的原料合成了两种新的以简单吡唑(C3H4N2简写为pz)为配体的不同钒氧配合物,VO(pz)4(SO4)．H2O(1)和V2O2(μ-pz)(μ-OOSO2)(μ-OCH3)(pz)4(2)．配合物1是单核的以4个吡唑为端配的钒氧配合物;配合物2是以吡唑阴离子、硫酸根和甲氧基为桥基的三元异桥双核配合物．对两个配合物进行了元素分析、红外光谱表征,并用X单晶衍射测定了配合物1和2的晶体结构．此外,进行了非等温热分解动力学研究．配合物1的晶体属于正交晶系,空间群:Pna21,a=14．547(2) A, b=10．895(2) A,C=11．835(2) A;α=β=γ=90°,V=1875．8(5) A3,Z=4,R1=0．0485,wR2=0．1092．对于配合物2:三斜晶系,空间群:P1,a=8．377(2) A,b=9．928(2) A,C=16．527(3) A,α=85．54(3)°,β= 80．92(3)°,γ=87．92(3),V=1352．7(5) A3,Z=2,R1=0．1461,wR2:0．4444．非等温热分解动力学研究表明,配合物1的第一阶段和第二阶段热分解反应可能的反应机理分别为成核与生长n=1／3,三维扩散n=2．配合物2第一阶段和第二阶段热分解反应可能的机理分别为化学反应,三维扩散n=2．
Two new vanadium complexes, VO (pz) 4 (SO4) with simple pyrazole (C3H4N2, abbreviated as pz) as ligands, were synthesized from the same starting materials at room temperature. H2O (1) and V2O2 (μ-pz) (μ-OOSO2) (μ-OCH3) (pz) 4 (2). Complex 1 is a mononuclear 4-pyrazole-terminated vanadate complex. Complex 2 is a ternary bridged binuclear complex with pyrazole anion, sulfate and methoxy as the bridge. The two complexes were characterized by elemental analysis and FTIR spectroscopy. The crystal structures of complexes 1 and 2 were determined by single crystal X-ray diffraction. In addition, kinetic studies of non-isothermal pyrolysis were carried out. The crystal of complex 1 belongs to the orthorhombic system. The space group: Pna21, a = 14.547 (2) A, b = 10.895 (2) A, C = 11.835 (2) A; γ = 90 °, V = 1875.8 (5) A3, Z = 4, R1 = 0.0485, wR2 = 0.1092. For the complex 2: triclinic, the space group: P1, a = 8.377 (2) A, b = 9.928 (2) A, C = 16.527 (3) A, α = 85.54 (3) °, β = 80.92 (3) °, γ = 87.92 (3), V = 1352.7 (5) A3, Z = 2, R1 = 0.1461, wR2: 0.4444. The kinetics of non-isothermal pyrolysis shows that the possible reaction mechanisms of the first and second phase of complex 1 are n = 1/3 for nucleation and growth, and n = 2 for three-dimensional diffusion. The possible mechanism of the thermal decomposition reaction of the first and second phases of complex 2 are respectively chemical reaction and three-dimensional diffusion n = 2.