Ternary copper(II) complexes with 1,10‑phenanthroline and various aminoacidates: A spectroscopic and voltammetric study in aqueous solution. 2019

Gabriele Valora, and Gabriella Munzi, and Raffaele P Bonomo
Dipartimento di Scienze Chimiche, Università degli Studi di Catania, Viale A. Doria 6, 95125 Catania, Italy.

Ternary copper(II) complexes with 1,10‑phenanthroline and the aminoacids l‑arginine, l‑aspartic acid, l‑histidine, l‑glutamic acid, l‑glutamine, l‑leucine, l‑lysine, l‑methionine, l‑phenylalanine, l‑tryptophan, l‑tyrosine, l‑valine, were studied in aqueous solution by means of UV-Vis-NIR spectrophotometry, EPR spectroscopy either at room or at low temperatures, and Square Wave Voltammetry. From the experimental data it is possible to conclude that most of these ternary complexes show a pseudo-octahedral geometry with a CuN3O in plane chromophore and two oxygen atoms coming from water molecules perpendicularly bound to the equatorial plane. An exception to this general behaviour is given by the ternary copper(II) complex with 1,10‑phenanthroline and histidine at pH value near the neutrality because of the terdentate nature of histidine when it coordinates by means of its histamine-like mode. In this case, evidence for a probable square-based pyramidal stereochemistry is given in support. At pH values around 5 the histidine behaves as bidentate ligand coordinating by its glycine-like mode, so as the copper(II) ternary complex with 1,10‑phenathroline shows the pseudo-octahedral geometry found for all the ternary complexes with the other aminoacids. Moreover the ternary complex species with histidine at pH 5 and 7 are in equilibrium with each other as a function of the aqueous solution pH value and the temperature. In fact, the examination of low temperature EPR spectra at pH near 7 revealed not only a square-based pyramid complex but also products of decomposition. These results were also confirmed by the trend found in the formal redox potentials by the voltammetric measurements on many of these ternary complexes.

UI MeSH Term Description Entries
D010618 Phenanthrolines Phenanthroline
D003300 Copper A heavy metal trace element with the atomic symbol Cu, atomic number 29, and atomic weight 63.55. Copper-63,Copper 63
D006863 Hydrogen-Ion Concentration The normality of a solution with respect to HYDROGEN ions; H+. It is related to acidity measurements in most cases by pH pH,Concentration, Hydrogen-Ion,Concentrations, Hydrogen-Ion,Hydrogen Ion Concentration,Hydrogen-Ion Concentrations
D000596 Amino Acids Organic compounds that generally contain an amino (-NH2) and a carboxyl (-COOH) group. Twenty alpha-amino acids are the subunits which are polymerized to form proteins. Amino Acid,Acid, Amino,Acids, Amino
D012996 Solutions The homogeneous mixtures formed by the mixing of a solid, liquid, or gaseous substance (solute) with a liquid (the solvent), from which the dissolved substances can be recovered by physical processes. (From Grant & Hackh's Chemical Dictionary, 5th ed) Solution
D013053 Spectrophotometry The art or process of comparing photometrically the relative intensities of the light in different parts of the spectrum.
D014867 Water A clear, odorless, tasteless liquid that is essential for most animal and plant life and is an excellent solvent for many substances. The chemical formula is hydrogen oxide (H2O). (McGraw-Hill Dictionary of Scientific and Technical Terms, 4th ed) Hydrogen Oxide
D055664 Electrochemical Techniques The utilization of an electrical current to measure, analyze, or alter chemicals or chemical reactions in solution, cells, or tissues. Electrochemical Technics,Electrochemical Technic,Electrochemical Technique,Technic, Electrochemical,Technics, Electrochemical,Technique, Electrochemical,Techniques, Electrochemical
D056831 Coordination Complexes Neutral or negatively charged ligands bonded to metal cations or neutral atoms. The number of ligand atoms to which the metal center is directly bonded is the metal cation's coordination number, and this number is always greater than the regular valence or oxidation number of the metal. A coordination complex can be negative, neutral, or positively charged. Metal Complexes,Complexes, Coordination,Complexes, Metal

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