Coordination modes of histidine. 4. Coordination structures in the copper(II)-L-histidine (1:2) system

The coordination structures of various species in the copper(II)-L-histidine (1:2) system in aqueous solution have been deduced by investigating the pH dependence of the electronic and circular dichroism spectra. The contribution to the spectra of the glycine-like and histamine-like binding modes of L-histidine has been determined by recording the spectra of the ternary system copper(II)-histamine-L-histidine (1:1:1) and copper(II)-amino acid-L-histidine (1:1:1), respectively, in neutral aqueous solutions. Apical binding to copper(II) by the donor atom on the histidine side chain can contribute significantly to the stabilization of each of the two basic histidine binding modes. It has been concluded that Cu(HL)2+ (L-histidine = HL), the major species below pH approximately 3, contains a glycine-like bound histidine ligand with an unbound imidazolium cation. The species Cu(HL)L+, which is prominent in the pH region near 4.5, contains a glycine-like bound histidine molecule, with protonated imidazole ring, and a histamine-like bound histidine molecule. CuL2, the major species at neutral pH, exists in solution as an equilibrium mixture of a mixed-type chelation structure, with a glycine-like and a histamine-like bound histidine ligand, and a structure containing both histidine ligands bound histamine-like. The species containing deprotonated imidazole nuclei, such as Cu(H-1L2)-, which predominates above pH approximately 11, show an increased contribution by structures containing glycine-like bound histidine compared with CuL2.