Portal de Periódicos da CAPES

Binary complexes of palladium(II) with peptides and ternary complexes of palladium(II) with peptides and nucleosides-nucleotides

1990; Elsevier BV; Volume: 104; Issue: 1 Linguagem: Inglês

10.1016/0010-8545(90)80038-u

1873-3840

Spyridoula Kasselouri, Achilleas Garoufis, M. Lamera-Hadjiliadis, Nick Hadjiliadis,

Corrosion Behavior and Inhibition

1H NMR spectroscopy was applied to study the reactions of cis-[Pd(L)(H2O)2]2+ complexes (L is en, pic and dpa) with the N-acetylated tripeptides L-methionylglycylglycine, MeCOMet–Gly–Gly, and glycyl–L-methionyl–glycine, MeCOGly–Met–Gly. All reactions were performed in the pH range 2.0–2.5 with equimolar amounts of the cis-[Pd(L)(H2O)2]2+ complex and the tripeptide at 60 °C. The hydrolytic reactions of the cis-[Pd(en)(H2O)2]2+, cis-[Pd(pic)(H2O)2]2+ and cis-[Pd(dpa)(H2O)2]2+ complexes with MeCOMet–Gly–Gly were regioselective and only the amide bond involving the carboxylic group of methionine was cleaved. However, in the reactions of these three Pd(II) complexes with MeCOGly–Met–Gly, two amide bonds, Met–Gly and MeCO–Gly, were cleaved. From UV–Vis spectrophotometry studies, it was found that the rate-determining step of these hydrolytic reactions is the monodentate coordination of the corresponding Pd(II) complex to the sulfur atom of the methionine side chain. The rate of the cleavage of these amide bonds is dependent on the nature of the bidentate coordinated diamine ligand L (en > pic > dpa). The hydrolytic reaction of cis-[Pd(L)(H2O)2]2+-type complexes with MeCOMet–Gly–Gly, containing the methionine side chain in the terminal position of the peptide, is regioselective while in the reaction of these Pd(II) complexes with MeCOGly–Met–Gly, none selective cleavage of the peptide occurs. This study contributes to a better understanding of the selective cleavage of methionine-containing peptides employing palladium(II) complexes as catalysts.