含有羧基配体的蝎型钒氧配合物的合成、结构及其热分解动力学  

Synthesis,Structure and Non-thermal Decomposition Kinetics of Scorpionates 0xovanadium Complexes with Carboxyl Acid Ligand

作　　者：张宝丽[1] 邢永恒[1] 葛茂发[2] 孙政[2] 李章朋[1] 韩晶[1] 牛淑云[1] 

机构地区：[1]辽宁师范大学化学化工学院,辽宁大连116029 [2]中国科学院化学研究所,北京100080

出　　处：《物理化学学报》2007年第11期1701-1706,共6页Acta Physico-Chimica Sinica

基　　金：教育部留学回国基金(2005-2007);国家自然科学基金(20571036;20771051);辽宁省教育基金(05L212)资助项目

摘　　要：设计合成了两种新型的以聚吡唑硼酸盐、氨基酸为配体的钒氧配合物VO[phCH_2CH(NH_2)COO][HB(pz)_3] (1)和VO(3,5-Me_2pz)[HB(3,5-Me_2pz)_3](CH_3COO)(2).通过元素分析、红外光谱对配合物进行了表征,并利用单晶X射线衍射技术解析了它们的结构.非等温热分解动力学研究表明,配合物1和2的热分解反应都是分两步进行的.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,dα/dT=(A/β)e^(-ElRY)(1/4)(1-α)[-ln(1-α)]^(-3)和dα/dT=(A/β)e^(-ElRT)(1-α)~2.分解反应的表观活化能分别是223.52和331.94 kJ·mol^(-1);指前因子ln(A/s^(-1))分别是49.67和57.50.配合物2热分解的第一步反应的可能机理为化学反应;第二步反应的可能机理为成核与生长(n=1/2).其非等温动力学方程分别为,dα/dT= (A/β)e^(-ElRT)(1-α)~2,和dα/dT=(A/β)e-^(-RlRT)(1/2)(1-α)[-ln(1-a)]^(-1).分解反应的表观活化能分别是300.56和444.72KJ·mol^(-1);指前因子ln(A/s^(-1))分别是75.53和92.50.Two new oxovanadium complexes with poly（pyrazolyl）borate and carboxylic acid as ligands, VO [phCH2CH （NH2）COO] [HB（pz）3] （1） and VO（3,5-Me2pz）[HB（3,5-Me2pz）3]（CH3COO） （2）, were synthesized successfully. The two complexes were characterized by IR, elemental analyses, thermal analyses, and single crystal X-ray diffraction. The study of non-isothermal decomposition kinetics for complex 1 showed that the possible reaction mechanisms of the two steps were nucleation and growth with n=1/4, and chemical reaction, respectively; the kinetic equations may be expressed as dcddT=（A/β）e^-EIRT（1/4）（1-α）[-ln（1-α）]^-δ and dα/dT=（A/β）e-EIRT（1-α）^2, respectively, the apparent activation energies of the steps are 223.52 and 331.94 kJ.mol^-1, respectively, the pre-exponentials ln（A/s^-1） are 49.67 as well as 57.50. The study of non-isothermal decomposition kinetics for complex 2 showed： the possible reaction mechanisms of the two steps were chemical reaction, and nucleation and growth with n=1/2, respectively, the kinetic equations may be expressed as dα/dT=（A/β）e-EIRT（1-α）^2, and dα/dT=（A/β）e-EIRT（1/2）（1-α）[-ln（1-α）]^-1, respectively, the apparent activation energies of the steps were 300.56 and 444.72 kJ. mol^-1, respectively, the pre-exponentials ln（A/s^-1） were 75.53 as well as 92.50.

关 键 词：钒氧配合物 聚吡唑硼酸盐 晶体结构 热分解动力学 

分 类 号：O641.4[理学—物理化学]