新型Salen型配合物的合成和表征及轴向配位热力学  

Synthesis and Characterization of Novel Salen-Type Complexes and Their Axial Coordination Thermodynamics

作　　者：郭莉芹[1] 史秀丽[1] 阮文娟[1] 张晓红[1] 朱志昂[1] 

机构地区：[1]南开大学化学学院,天津300071

出　　处：《物理化学学报》2010年第5期1195-1201,共7页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金(20671053)资助项目~~

摘　　要：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(1HNMR)、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K苓(Im)>K苓(N-MeIm)>K苓(2-Et-4-MeIm)>K苓(2-MeIm)顺序依次减小;测得的△rHm苓和△rSm苓数据表明该轴向配位反应为放热、熵增加过程.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 transform infrared（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（NMeIm） were 2,but for 2-Et-4-MeIm and 2-MeIm they were 1.The association constants of the systems decrease according to the following order：K（Im） 〉K（N-MeIm） 〉K（2-Et-4-MeIm）〉 K（2-MeIm）.The thermodynamic parameters △rHm and △rSm were also determined.Results showed that the axial coordination process was driven by enthalpy and entropy.

关 键 词：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 

分 类 号：O641.4[理学—物理化学]