蝎型铜配合物:Cu_2[μ-pz]_2[HB(pz)_3]_2和Cu[B(pz)_4]_2的合成、结构及热分解动力学性质  

Scorpionates Copper Complexes Cu_2μ-pz_2HB(pz)_3_2 and CuB(pz)_4_2: Synthesis, Structure and Thermal Decomposition Kinetics Properties

作　　者：邢永恒[1] 张兴晶[1] 韩晶[1] 张元红[1] 白凤英[1] 牛淑云[1] 

机构地区：[1]辽宁师范大学化学化工学院,大连116029

出　　处：《无机化学学报》2007年第7期1143-1147,共5页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.20571036);留学回国基金(No.2005-2007);辽宁省教育基(No.05L212)资助项目

摘　　要：本文设计合成了两种以聚吡唑硼酸盐、吡唑为配体的铜配合物Cu2[μ-pz]2[HB(pz)3]2(1)和Cu[B(pz)4]2(2)(pz:吡唑(C3H4N2))。运用元素分析、红外光谱对配合物进行了表征,并用X-ray衍射测定了它们的晶体结构。非等温热分解动力学研究表明:配合物1的热分解反应分两步,配合物2的热分解反应一步进行。通过计算,配合物1热分解的第一步反应的可能机理为成核与生长,n=1/4;第二步反应的可能机理为化学反应。其非等温动力学方程分别为:dd"T=A#e-RET·41(1-α)[-ln(1-α)]-3和dd"T=A$e-RET(1-α)2。分解反应的表观活化能分别是520.37kJ·mol-1和149.65kJ·mol-1;指前因子lnA分别是118.06s-1和28.10s-1。配合物2热分解的可能机理为化学反应。其非等温动力学方程为:dd"T=A$e-RET(1-α)2。分解反应的表观活化能是111.41kJ·mol-1;指前因子lnA是21.20s-1。Two copper complexes, Cu2[μ-pz]2[HB（pz）3]2（1） and Cu[B（pz）4]2（2） （pz： pyrazole （C3H4N2））, with poly （pyrazolyl）borate and pyrazole as ligands, were synthesized successfully. The two complexes were characterized by IR, elemental analyses, thermal analyses and X-ray diffraction. The study of thermal decomposition kinetics for complex 1 show： the decomposition process is two steps, and the corresponding possible reaction mechanisms are nucleation and growth （n=l/4）, and chemical reaction, respectively; the non-isothermal kinetic equations may be expressed da/dT=A/βe^-E/RT·1/4（1-α）[-ln（1-α）]^-3 and da/dT=A/βe^RET（1-α）^2, respectively; the apparent activation energy is 520.37 kJ.mol^-1 and 149.65kJ·mol^-1, respectively; the pre-exponentials are 118.06s^-1and28.10s^-1. The study of thermal decomposition kinetics for complex 2 shows： the possible reaction mechanisms of only a step is chemical reaction, the non-isothermal kinetic equations may be expressed as da/dT=（A/β＊e^E/RT＊）（1-α）^2 ; the apparent activation energy is 111.41kJ·mol^-1; the pre-exponentials is 21.20s^-1. CCDC： 621240, 1.

关 键 词：铜配合物 聚吡唑硼酸盐 吡唑 晶体结构 热分解动力学 

分 类 号：O614.121[理学—无机化学]