Citation: GUO Li-Qin, SHI Xiu-Li, RUAN Wen-Juan, ZHANG Xiao-Hong, ZHU Zhi-Ang. Synthesis and Characterization of Novel Salen-Type Complexes and Their Axial Coordination Thermodynamics[J]. Acta Physico-Chimica Sinica, 2010, 26(05): 1195-1201. doi: 10.3866/PKU.WHXB20100336
新型Salen型配合物的合成和表征及轴向配位热力学
采用金属模板法合成了四个新型Salen型单、双核金属配合物, 并用元素分析、核磁共振(1H NMR)、电喷雾质谱(ESI-MS)、傅里叶变换红外光谱(FT-IR)等手段进行了表征. 使用紫外-可见(UV-Vis)光谱滴定法和圆二色(CD)光谱研究了主体金属镍配合物与咪唑类含氮小分子的轴向配位反应热力学性质. 结果表明: 主体与咪唑(Im)和N-甲基咪唑(N-MeIm)的配位数是2, 而与2-Et-4-MeIm和2-MeIm的配位数是1; 轴配体系的热力学数据显示主体与咪唑类配体的平衡常数按KΘ(Im)>KΘ(N-MeIm)>KΘ(2-Et-4-MeIm)>KΘ(2-MeIm)顺序依次减小; 测得的△rHΘm 和△rSΘm数据表明该轴向配位反应为放热、熵增加过程.
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关键词:
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金属模板法
- / 新型Salen型配合物
- / 合成表征
- / 轴向配位热力学
- / 圆二色光谱
English
Synthesis and Characterization of Novel Salen-Type Complexes and Their Axial Coordination Thermodynamics
Four novel Salen-type mono-and bi-nuclear complexes were synthesized by a metal template method, and were characterized by elemental analyses, hydrogen nuclear magnetic resonance (1H NMR), electrospray ionization mass spectroscopy (ESI-MS), Fourier transforminfrared (FT-IR) spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy, and circular dichroism(CD)spectroscopy. The thermodynamic behavior of the Salen-type Ni (II) complexes were studied by UV-Vis and CD spectra. We found that the coordination numbers for imidazole (Im) and N-methylimidazole (N-MeIm)were 2, but for 2-Et-4-MeImand 2-MeImthey were 1. The association constants of the systems decrease according to the following order: KΘ(Im) >KΘ(N-MeIm) >KΘ(2-Et-4-MeIm) >KΘ(2-MeIm). The thermodynamic parameters △rHΘm and △rSΘm were also determined. Results showed that the axial coordination process was driven by enthalpy and entropy.
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