摘要
At room temperature, two new different oxovanadium complexes with simple pyrazole (C3H4N2) as ligand were synthesized. VO(pz)4(SO4)? H2O (1) (pz: pyrazole) is a mono-nuclear oxovana- dium complex with pyrazole as terminal ligands. V2O2(μ-pz)(μ-OOSO2)(μ-OCH3)(pz)4 (2) is bi-nuclear oxovanadium complex containing three different bridges, which are pyrazolate, sulphate and methoxy, respectively. The two complexes were characterized by IR, elemental analyses, thermal analyses and X-ray diffraction. The crystal structural data of the complexes 1 and 2 are given as follows: Complex 1, orthorhombic, Pna21, a = 14.547(2) ?, b =10.895(2) ?, c =11.835(2) ?; α=β=γ=90°, V=1875.8(5) ?3, Z = 4, R1 = 0.0485, WR2 = 0.1092. Complex 2, triclinic, P1 , a =8.377(2) ?, b =9.928(2) ?, c = 16.527(3) ?, α = 85.54(3)°, β = 80.92(3)°, γ = 87.92(3)°, R1 = 0.1461, WR2 = 0.4444. The study of non-thermal kinetic de- composition shows that, for complex 1, the possible reaction mechanisms of the two steps are nucleation and growth n=1/3, and three-dimensional pervasion n=2, respectively, and the kinetic equations may be expressed as dα/dT = (A/β)exp(?E/RT){1/3(1?α) [?In(1?α)]?2} and dα/dT = (A/β)exp(?E/RT){3/2(1?α)2/3 [1?(1?α)1/3] ?1}, respectively; for complex 2, the pos- sible reaction mechanisms of the two steps are chemical reaction, and three-dimensional pervasion n=2, respectively; the kinetic equations may be ex- pressed as dα/dT = (A/β)exp(?E/RT)[(1?α)2], anddα/dT = (A/β)exp(?E/RT){3/2(1?α)2/3[1?(1?α)1/3] ?1}, respectively.
Abstract At room temperature, two new different oxovanadium complexes with simple pyrazole （C3H4N2） as ligand were synthesized. VO（pz）4（SO4）·H2O （1） （pz： pyrazole） is a mono-nuclear oxovanadium complex with pyrazole as terminal ligands. V2O2（μ-pz）（μ-OOSO2）（μ-OCH3）（pz）4 （2） is bi-nuclear oxovanadium complex containing three different bridges, which are pyrazolate, sulphate and methoxy, respectively. The two complexes were characterized by IR, elemental analyses, thermal analyses and X-ray diffraction. The crystal structural data of the complexes 1 and 2 are given as follows： Complex 1, orthorhombic, 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. Complex 2, triclinic, 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）°,R1 = 0.1461, wR2 = 0.4444. The study of non-thermal kinetic decomposition shows that, for complex 1, the possible reaction mechanisms of the two steps are nucleation and growth n=1/3, and three-dimensional pervasion n=2, respectively, and the kinetic equations may be expressed as dα/dT = （Aβ）exp（-E/RT）{1/3（1-α）{-In（1-α）]^-2} and dα/d T= （A/β）exp（-E/RT）{3/2（1-α）^2/3 {1-（1-α）^1/3]^-1}, respectively; for complex 2, the pos- sible reaction mechanisms of the two steps are chemical reaction, and three-dimensional pervasion n=2, respectively; the kinetic equations may be expressed as dα/dT = （A/β）exp（-E/RT）[（1-α）^2], and dα/d T = （A/β）exp（-E/RT）{3/2（1-α）^2/3[1 -（1-α）^1/3]^-1}, respectively.
基金
the National Natural Science Foundation of China （Grant No. 20571036）, SPF（2004-2007） for R0CS
SEM and Education Foundation of Liaoning Province （Grant No. 05L212）.
