The binary complexes of Hg2+ formed by N-carbonyl and N-sulfonyl amino acids, which are ligands containing peptide and sulfonamide groups respectively, are investigated in aqueous solution by H-1 NMR, UV spectroscopy and potentiometry. The corresponding ternary systems with 2,2'-bipyridine are studied in aqueous solution by potentiometry and in DMSO solutions by H-1-NMR. All the amino acids behave as simple carboxylate ligands at acid pH, while, around neutrality, N-p-tolylsulfonylglycine (tsglyH(2)), N-p-tolylsulfonyl-beta -alanine (ts-beta -alaH(2)) and N-2-nitrophenylsulfonylglycine (NO(2)psglyH(2)) switch to dianionic N,O-bidentate chelating ligands due to the involvement of the deprotonated amide nitrogen as an additional donor site. The Hg2+ ion is ineffective in promoting peptide nitrogen deprotonation in N-benzoylglycine (bzglyH). The binary and ternary species formed in aqueous solution and their stability constants are determined and compared with those of the homologous complexes of Pd2+, Cu2+, Cd2+ and Pb2+. The molecular structure of [Hg(bpy)(2)(NO2-psgly-N,O)].0.5H(2)O is determined by X-ray crystallography. It represents a rare example of Hg2+ N,O coordination by an amino acid molecule. In the complex Hg2+ shows a distorted octahedral environment with a N5O donor set. Four nitrogen atoms are derived from the two bpy ligands, while the oxygen and the fifth nitrogen are from the NO2-psgly dianion. New information on the solution and solid state chemistry of Hg2+ with ligands of biological interest is provided which may be of great relevance in understanding the mechanism of metal toxicity.
|Anno di pubblicazione:||2001|
|Titolo:||Amide group coordination to the Hg2+ ion. Potentiometric, 1H NMR and structural study on Hg2+-N-protected amino acid systems|
|Autori:||M. Saladini; L. Menabue; E. Ferrari; D. Iacopino|
|Appare nelle tipologie:||Articolo su rivista|
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