Ferrocene substitution in amino acids strengthens the axial binding in Cu(ii) complexes and separates the hydrophobic and hydrophilic region in the crystals

Abstract

This paper reports on the synthesis, characterization and electrochemical properties of four ferrocenylmethyl substituted L-amino acid ligands and their Cu(II) complexes. Structural characterization of the complexes of L-methionine and L-asparagine derived ligands showed axial coordination of weak thioether and amide respectively to Cu(II). Coordination of the thioether group of L-methionine to copper (2.791 Å) is shorter than observed in the electron transfer protein plastocyanin (2.9 Å). Methionine thioether does not bind in synthetic Cu(II) complexes. The characterization of bis-complexes (metal : ligand ratio 1 : 2) with L-serine and L-threonine derivatives showed axial coordination of water with a shorter Cu–O bond length compared to that observed in the corresponding amino acid complexes. The structures also revealed separation of the hydrophilic and hydrophobic regions due to amino acid and ferrocene respectively which resulted in the formation of interesting H-bonded networks.