| 蝎型铜配合物：Cu2[ 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 Cu2[ μ-pz]2[HB(pz)3]2 and Cu[B(pz)4]2: Synthesis, Structure and Thermal Decomposition Kinetics Properties |
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| 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：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520.37 kJ·mol-1和149.65 kJ·mol-1；指前因子lnA分别是118.06 s-1和28.10 s-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：dα/dT=A/β e-E/RT·(1-α)2。分解反应的表观活化能是111.41 kJ·mol-1；指前因子lnA是21.20 s-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 |
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| Abstract: 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=1/4), and chemical reaction, respectively; the non-isothermal kinetic equations may be expressed 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 energy is 520.37 kJ·mol-1 and 149.65 kJ·mol-1, respectively; the pre-exponentials are 118.06 s-1 and 28.10 s-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 dα/dT=A/β e-E/RT·(1-α)2; the apparent activation energy is 111.41 kJ·mol-1; the pre-exponentials is 21.20 s-1. CCDC: 621240, 1. |
| Keywords: copper complexes poly(pyrazolyl)borate pyrazole crystal structure thermal decomposition kinetics |
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| 邢永恒,张兴晶,韩晶,张元红,白凤英,牛淑云.蝎型铜配合物：Cu2[ 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[J].无机化学学报,2007,23(7):1143-1147. |
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