title: Donor atom electrochemical contribution to redox potentials of square pyramidal vanadyl complexes.
abstract: A simple donor atom additivity relationship has been used to calculate the donor atom electrochemical contribution (DEC) of the Oac (acetylacetonate-enolic oxygen), OPh (phenolic oxygen), SPh (mercaptophenol sulfur), Nam (deprotonate amide nitrogen), Nim (imine nitrogen) and Npy (pyridine nitrogen) to the redox processes of the square pyramidal vanadyl complexes. The study focuses on the amidate vanadyl complexes because of (a) their biological interest and (b) the existence of data from plethora complexes studied in great details. The electrochemical contributions for the vanadyl oxidation and reduction processes increase following the same order, OPh~Oac(enolic)<SPh~Nam<Nim<Npy. These values predict the electrochemical potentials of square pyramidal vanadyl complexes with high accuracy. Octahedral complexes with the same equatorial environment show significant shift of the oxidation potentials to lower values. The DEC influence to the square pyramidal vanadyls' electrochemical potentials has been evaluated.
authors: Department of Chemistry, University of Cyprus, 1678 Nicosia, Cyprus.
authors: Manolis
authors: M
authors: Vlasiou
authors: Department of Agricultural Sciences, Biotechnology and Food Science, Cyprus University of Technology, Lemesos 3036, Cyprus. Electronic address: chryssoula.drouza@cut.ac.cy.
authors: Chryssoula
authors: C
authors: Drouza
authors: Department of Chemistry, Section of Inorganic and Analytical Chemistry, University of Ioannina, 45110 Ioannina, Greece. Electronic address: tkampano@cc.uoi.gr.
authors: Themistoklis A
authors: TA
authors: Kabanos
authors: Department of Chemistry, University of Cyprus, 1678 Nicosia, Cyprus. Electronic address: akeramid@ucy.ac.cy.
authors: Anastasios D
authors: AD
authors: Keramidas
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D013455:Sulfur / Q000737:chemistry; D014638:Vanadates / Q000737:chemistry*; D014639:Vanadium / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D014639:Vanadium; D014638:Vanadates; D013455:Sulfur; D009584:Nitrogen; D010100:Oxygen
keywords: Additivity rule; Cyclic voltammetry; Electrochemistry; Potential prediction; Vanadium; Vanadyl