新型多氨-多酰氨配体和氨基酸的三元铜(Ⅱ)配合物(英文)  

Ternary Copper(Ⅱ) Complexes of Novel Polyamino-polyamide Ligands and Amino-acids

作　　者：郭延河[1] 盖庆春[1] 李风华[1] 林华宽[1] 朱守荣[1] 

机构地区：[1]南开大学化学系,天津300071

出　　处：《无机化学学报》2004年第4期381-388,共8页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金资助项目(No.20371028);天津市自然科学基金资助项目(No.023605811)。

摘　　要：合成3个多氨鄄多酰氨配体1,12鄄二((α鄄羟甲基)苯基)鄄2,5,8,11鄄四氮杂十二烷鄄1,12鄄二酮(L1),1,13鄄二((α鄄羟甲基)苯基)鄄2,5,9,12鄄四氮杂十三烷鄄1,13鄄二酮(L2),1,15鄄二((α鄄羟甲基)苯基)2,5,8,11,14鄄五氮杂十五烷鄄1,15鄄二酮(L3)。利用pH滴定分别在5.0℃,15.0℃,25.0℃,35.0℃测定了铜髤与这3种配体在二氧六环/水(V/V,15/85)混合溶剂中配位的稳定常数,得到了热力学参数驻H苓m和驻S苓m。其结果显示了配体的质子化和金属配合物的形成受到焓变化的控制。此外,在25.0℃测定了铜(II),配体L和氨基酸(AA)三元配合物的稳定常数,其中L=L1,L2和L3,AA=L鄄脯氨酸(Pro),L鄄异亮氨酸(Ile),L鄄缬氨酸(Val),甘氨酸(Gly),L鄄丝氨酸(Ser)。观察到在三元体系中存在着直线自由能关系(LFER)。Three polyamino-polyamide ligands1,12-bis(( α -hydroxylmethyl)phenyl)-2,5,8,11-tetraazadodecane-1,12-dione(L 1 ),1,13-bis(( α -hydroxylmethyl)phenyl)-2,5,9,12-tetraazatridecane-1,13-dione(L 2 ),1,15-bis(( α -hydroxylmethyl)phenyl)-2,5,8,11,14-pentaazapentadecane-1,15-dione(L 3 )have been synthesized.The stability constants of com-plexation of Cu (Ⅱ) with these three ligands in dioxane/water(V/V,15/85)mixed solvent have been determined by pH titrations at5.0℃,15.0℃,25.0℃and35.0℃respectively.The thermodynamic parameters Δ H m and S m were obtained.The result shows that both the protonation of the ligands and the formation of metal complexes are controlled by the change of enthalpy.In addition,the stability constants of ternary complexes of Cu (Ⅱ) ,L and -amino-acid(AA)have been determined at25.0℃,where L=L 1 ,L 2 and L 3 ,AA=L-proline(Pro),L-isoleucine(Ile),L-valine(Val),glycine(Gly),L-serine(Ser),respectively.It is observed that linear free energy relationship(LFER)exists in the ternary systems.

关 键 词：多氨-多酰氨配体 氨基酸 三元配合物 铜配合物 热力学 稳定常数 直线自由能关系 

分 类 号：O614.121[理学—无机化学] O623.736[理学—化学]