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 Pd2+, Cu2+, Cd2+, and Zn2+. The Pb2+ 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)(H2O)] (1), [Pb(N-benzoylglycinato-O)(2)-(H2O)(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 Pb2O2 square-planar rings. The binding set in 1, involving a deprotonated amide nitrogen and a sulfonic oxygen, is unprecedented for the Pb2+ 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.

Amide group coordination to the Pb2+ ion / BATTISTUZZI, Gianantonio; BORSARI, Marco; MENABUE, Ledi; SALADINI, Monica; SOLA, Marco. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - STAMPA. - 35:(1996), pp. 4239-4247.

Amide group coordination to the Pb2+ ion

BATTISTUZZI, Gianantonio;BORSARI, Marco;MENABUE, Ledi;SALADINI, Monica;SOLA, Marco
1996-01-01

Abstract

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 Pd2+, Cu2+, Cd2+, and Zn2+. The Pb2+ 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)(H2O)] (1), [Pb(N-benzoylglycinato-O)(2)-(H2O)(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 Pb2O2 square-planar rings. The binding set in 1, involving a deprotonated amide nitrogen and a sulfonic oxygen, is unprecedented for the Pb2+ 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.
35
4239
4247
Amide group coordination to the Pb2+ ion / BATTISTUZZI, Gianantonio; BORSARI, Marco; MENABUE, Ledi; SALADINI, Monica; SOLA, Marco. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - STAMPA. - 35:(1996), pp. 4239-4247.
BATTISTUZZI, Gianantonio; BORSARI, Marco; MENABUE, Ledi; SALADINI, Monica; SOLA, Marco
File in questo prodotto:
Non ci sono file associati a questo prodotto.
Pubblicazioni consigliate

Licenza Creative Commons
I metadati presenti in IRIS UNIMORE sono rilasciati con licenza Creative Commons CC0 1.0 Universal, mentre i file delle pubblicazioni sono rilasciati con licenza Attribuzione 4.0 Internazionale (CC BY 4.0), salvo diversa indicazione.
In caso di violazione di copyright, contattare Supporto Iris

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/305019
Citazioni
  • ???jsp.display-item.citation.pmc??? 3
  • Scopus 87
  • ???jsp.display-item.citation.isi??? 88
social impact