Theoretical evidence of the Ni(III) participation in the chlorophenol oxidation on tetrasulphonated nickel phthalocyanine

摘要

A theoretical methodology at B3LYP/LACVP(d)++ level for describing the oxidation of six chlorophenols (CP) on a nickel tetrasulphonated phthalocyanine (NiTSPc) is presented. The chlorophenols studied are: 2-chlorophenol (2-CP), 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-CP), 2,6-dichlorophenol (2,6-CP), 2,4,6-trichlorophenol (2,4,6-CP), and pentachlorophenol (P-CP). On the basis of the experimental facts obtained by cyclic voltammetry, where the CP oxidation was carried out on poly-NiTSPc modified glassy carbon electrodes, the different stages (A-D) produced along the oxidation-reduction process were characterized at theoretical level, thereby obtaining their molecular and electronic structures. We found that the stage C, represented by the interaction of a chlorophenol anion with the Ni(III) complex shows, except in 2,4-CP and P-CP, the CP oxidation in all chlorophenols. These results predict Ni(III) to be the oxidation state that produce the oxidation of chlorophenol, in complete agreement with the experimental results. Natural bonds analysis gives evidence for explaining why 2,4-CP and P-CP do not show a CP oxidation. A strong delocalization toward a alpha-carbon of the phenolic ring from a beta-carbon (206.31 kcal/mol for 2,4 CP, 200.66 kcal/mol for P-CP) and from the oxygen atom (58.67 kcal/mol for 2,4-CP, 83.91 kcal/mol for P-CP) seems to be the responsible for avoiding the CP oxidation with the Ni(III) complex. (C) 2008 Wiley Periodicals, Inc. Int J Quantum Chem 108: 2586-2594, 2008.