手性双核Salen配合物的谱学性质  

Study on Spectra Properties of Chiral Dinuclear Salen Complex

作　　者：胡国航[1] 阮文娟[1] 张玉玲[1] 韩华[1] 朱志昂[1] 

机构地区：[1]南开大学化学系,天津300071

出　　处：《物理化学学报》2003年第4期320-325,共6页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金(20171024);天津市自然科学基金(No.0023604011);回国人员研究基金资助项目~~

摘　　要：合成了四个新型的手性双核(R,R)Salen配合物犤(Cu)2L·H2O(2),(Ni)2L(3),(Zn)2L·H2O(4),(MnCl)2L·2H2O(5)犦,(其中L是由(R,R)环己二胺、3,5-叔丁基水杨醛、5,5'-亚甲基二水杨醛为原料合成的手性二聚Salen配体(1)).用元素分析、NMR、FT-IR、UV-Vis、CD光谱对配体和配合物进行了表征.在与单核的Salen配体和配合物比较的基础上,详细讨论了红外光谱、电子吸收光谱、圆二色光谱性质.发现双核配体和配合物的电子吸收光谱吸收峰的位置和形状与单核的配体和配合物基本一致,而吸收峰的强度有近似两倍的关系.另外,用激子偶合理论解释了此类手性化合物圆二色谱的Cotton效应和Cotton分裂.Cot-ton分裂的方向依赖于环己二胺的构象.(R,R)环己二胺决定了Salen化合物的手征性为负,Cotton分裂的正负两部分分别处于高能区和低能区.Four novel chiral dinuclear Salen complexes [(Cu)(2)(LH2O)-H-.(2), (Ni)(2)L(3), (Zn)(2)(LH2O)-H-.(4), (MnCl)(2)L (.) 2H(2)O(5)] have been synthesized (L is chiral dimeric Salen ligand which is synthesized from (R, R) -diaminocyclohexane, 3, 5-di-tert-butyl salicylaldehyde, 5, 5'-methylene-di-salicylaldehyde). These ligands and complexes were characterized by elemental analysis, H-1 NMR, UV-Vis, FT-IR, CD spectra. The UV-Vis spectra were compared with those of monomeric Salen ligand and complex. It was found that the position and shape of absorption band are similar to those of the corresponding monomeric compounds, but the values of the absorption peak(epsilon) are approximately two foldes larger. Furthermore Cotton effect and Cotton split of CD spectra of these chiral compounds were explained by the exciton interaction theory. It seemed that the direction of Cotton split depend on the configuration of diaminocyclohexane. (R, R)-diaminocyclohexane termined the chirality of Salen compounds as negative, and the positive and negative component of Cotton split lie at higher and lower energy repectively.

关 键 词：手性双核Salen配合物 谱学性质 催化性能 不对称催化剂 手性金属配合物 

分 类 号：O641.4[理学—物理化学]