ISSN:
0009-2940
Keywords:
Hydrogen bis-L-pyroglutamates, lithium, sodium, potassium
;
Pyroglutamate coordination and conformation
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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 1H- and 13C—NMR investigations of aqueous solutions of the compounds indicate extensive electrolytic dissociation in dilute solutions.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19921250808
