Synthesis and characteriza-tion of two new types of oxovanadium complexes with pyrazole as ligand

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.