物理化学学报 >> 2007, Vol. 23 >> Issue (11): 1701-1706.doi: 10.3866/PKU.WHXB20071109

研究论文 上一篇    下一篇

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

张宝丽; 邢永恒; 葛茂发; 孙政; 李章朋; 韩晶; 牛淑云   

  1. 辽宁师范大学化学化工学院, 辽宁 大连 116029; 中国科学院化学研究所, 北京 100080
  • 收稿日期:2007-06-18 修回日期:2007-07-12 发布日期:2007-11-01
  • 通讯作者: 邢永恒 E-mail:yhxing2000@yahoo.com

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

ZHANG Bao-Li; XING Yong-Heng; GE Mao-Fa; SUN Zheng; LI Zhang-Peng; HAN Jing; NIU Shu-Yun   

  1. College of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, Liaoning Province, P. R. China; Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, P. R. China
  • Received:2007-06-18 Revised:2007-07-12 Published:2007-11-01
  • Contact: XING Yong-Heng E-mail:yhxing2000@yahoo.com

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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[phCH2CH(NH2)COO][HB(pz)3](1)和VO(3,5-Me2pz)[HB(3,5-Me2pz)3](CH3COO)(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-E/RT(1/4)(1-α)[-ln(1-α)]-3 和dα/dT=(A/β)e-E/RT(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-E/RT(1-α)2, 和dα/dT=(A/β)e-E/RT(1/2)(1-α)[-ln(1-α)]-1. 分解反应的表观活化能分别是300.56 和444.72 kJ·mol-1; 指前因子ln(A/s-1)分别是75.53 和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

Abstract: Twonewoxovanadiumcomplexes withpoly(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 dα/dT=(A/β)e-E/RT(1/4)(1-α)[-ln(1-α)]-3 and dα/dT=(A/β)e-E/RT(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-E/RT(1-α)2, and dα/dT=(A/β)e-E/RT(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.

Key words: Vanadiumcomplex, Poly(pyrazolyl)borate, Crystal structure, Thermal decomposition kinetics