Amide Group Coordination to the Pb(2+) Ion.
The binary and ternary (2,2'-bipyridine) complexes of dipositive lead formed by N-carbonyl and N-sulfonyl amino acids, which are ligands containing the peptide and the sulfonamide group, respectively, were investigated in aqueous solution by NMR and differential pulse polarography, and some were also characterized crystallographically. N-Tosylglycine, N-tosyl-beta-alanine, and N-benzoylglycine behave as simple carboxylate ligands at acid pH, while around neutrality they switch to dianionic N,O-bidentate chelating ligands due to the involvement of the deprotonated amide nitrogen as an additional donor site. The same coordination behavior is maintained in the presence of 2,2'-bipyridine. The binary and ternary species formed in solution, and their stability constants were determined and compared with those of the homologous complexes of Pd(2+), Cu(2+), Cd(2+), and Zn(2+). The Pb(2+) ion is the only dipositive metal which is effective in promoting peptide nitrogen deprotonation in benzoylglycine. The molecular structures of [Pb(N-tosylglycinato-N,O)(H(2)O)] (1), [Pb(N-benzoylglycinato-O)(2)(H(2)O)(2)].2H(2)O (2), and [Pb(N-tosylglycinato-O)(2)(bpy)] (3) were determined by X-ray crystallography (O and N,O refer to the ligands binding as carboxylates and as N,O-chelating dianions, respectively). These compounds are all polymeric with six- to eight-coordinate metals showing distorted coordination geometries indicative of a stereochemically active metal lone pair. Polymerization is invariably determined by a bidentate chelate carboxylate group with one oxygen bridging between two metals, and in 2 and 3 it occurs through the formation of chains of Pb(2)O(2) square-planar rings. The binding set in 1, involving a deprotonated amide nitrogen and a sulfonic oxygen, is unprecedented for the Pb(2+) ion. This work provides new information on the solution and solid state chemistry of dipositive lead with ligands of biological interest, a research area that has received little attention in the past, although it is of great relevance for understanding the mechanisms of metal toxicity.
Battistuzzi
Gianantonio
G
Institute of Agricultural Chemistry, University of Bologna, Viale Berti Pichat 10, 40127 Bologna, Italy.
Borsari
Marco
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Menabue
Ledi
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Saladini
Monica
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Sola
Marco
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