METAL-BINDING BY AMINO-ACIDS - PREPARATION AND CRYSTAL-STRUCTURES OF LITHIUM, SODIUM, AND POTASSIUM HYDROGEN BIS-L-PYROGLUTAMATE

被引:6
作者
KUMBERGER, O [1 ]
RIEDE, J [1 ]
SCHMIDBAUR, H [1 ]
机构
[1] TECH UNIV MUNICH,INST ANORGAN CHEM,LICHTENBERGSTR 4,W-8046 GARCHING,GERMANY
来源
CHEMISCHE BERICHTE-RECUEIL | 1992年 / 125卷 / 08期
关键词
HYDROGEN BIS-L-PYROGLUTAMATES; LITHIUM; SODIUM; POTASSIUM; PYROGLUTAMATE COORDINATION AND CONFORMATION;
D O I
10.1002/cber.19921250808
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Lithium, sodium and potassium hydrogen bis-L-pyroglutamate [Li(L-pGlu)(L-pGluH)], [Na(L-pGlu)(L-pGluH)] and [K(L-pGlu)(L-pGluH)], respectively, have been prepared by reaction of aqueous solutions of the metal hydroxides with L-pyroglutamic acid in the molar ratio 1:2, or in methanol. Crystalline samples of the salts could be obtained by slow evaporation of solutions of the salts in methanol. In the solid state, Li(L-pGlu)(L-pGluH) adopts a chain structure with the lithium atoms arranged in double strands. Adjacent metal centers are bridged by the carboxylate groups of the L-pGlu- ligands. The L-pGluH ligands are attached to the metal centers through the amide oxygen atoms. Na(L-pGlu)(L-pGluH) forms a three-dimensional coordination polymer with two half-occupied sodium positions, one L-pGlu- and one L-pGluH ligand in the asymmetric unit. The carboxyl and carboxylate groups of the L-pGluH and the L-pGlu- ligands are bridging the sodium centers, giving rise to eight-membered rings, which consist of two sodium atoms, a carboxyl and a carboxylate group. The hydrogen atoms of the carboxyl group of the L-pGluH ligands are involved in strong hydrogen bonds between a carboxyl and an adjacent carboxylate oxygen atom. K(L-pGlu)(L-pGluH) adopts a layer structure with strands of potassium atoms. The metal centers are connected through bridging carboxyl and carboxylate groups of the L-pGluH and L-pGlu- ligands, respectively. The structure features eight-membered ring units comparable to those observed for Na(L-pGlu)(L-pGluH), again with the hydrogen atom of the carboxyl group engaged in a strong transannular hydrogen bond. The amide oxygen atoms of the L-pGlu- and the L-pGluH ligands are coordinated to the metal centers of adjacent coordination chains. The results of H-1- and C-13-NMR investigations of aqueous solutions of the compounds indicate extensive electrolytic dissociation in dilute solutions.
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页码:1829 / 1834
页数:6
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