Directed coordination study of [Pd(en)(H2O)2]2+ with hetero-tripeptides containing C-terminus methyl esters employing NMR spectroscopy

Abstract

Alkylation of the C-terminus acids in small peptides allows direction to amine and amide coordination, while changing the peptide composition to form tetradentate κ4[n,5,5], where n = 5-, 6-, 7-, or 8-membered ring coordination geometries, can be achieved. The alkylated tripeptide ligands, TrpAlaGly(OMe), β-Asp(OtBu)AlaGly(OMe), Asp(OtBu)AlaGly(OMe), and the fully methylated GSH, γ-Glu(OMe)Cys(SMe)Gly(OMe), were synthesized and their coordination properties to [Pd(en)(H2O)2]2+ were studied. pH-dependent coordination was analyzed by NMR spectroscopy and the coordination to the alkylated tripeptides at selected pH values inferred from their NMR spectra. If selective coordination of amine/amide donors results in metal complexation, allowing for flexible and adjustable ligand frameworks, then this strategy could potentially be extended to other metal ions and peptide system.