title: Electron transfer reactions between copper(II) porphyrin complexes and various oxidizing reagents in acetonitrile.
abstract: Homogeneous electron transfer reactions of the Cu(II) complexes of 5,10,15,20-tetraphenylporphyrin (TPP) and 2,3,7,8,12,13,17,18-octaethylporphyrin (OEP) with various oxidizing reagents were spectrophotometrically investigated in acetonitrile. The reaction products were confirmed to be the pi-cation radicals of the corresponding Cu(II)-porphyrin complexes on the basis of the electronic spectra and the redox potentials of the complexes. The rate of the electron transfer reaction between the Cu(II)-porphyrin complex and solvated Cu(2+) was determined as a function of the water concentration under the pseudo first-order conditions where Cu(2+) is in large excess over the Cu(II)-porphyrin complex. The decrease in the pseudo first-order rate constant with increasing the water concentration was attributed to the stepwise displacement of acetonitrile in [Cu(AN)(6)](2+)(AN = acetonitrile) by water, and it was concluded that only the Cu(2+) species fully solvated by acetonitrile, [Cu(AN)(6)](2+), possesses sufficiently high redox potential for the oxidation of Cu(ii)-OEP and Cu(ii)-TPP. The reactions of the Cu(II)-porphyrin complexes with other oxidizing reagents such as [Ni(tacn)(2)](3+)(tacn = 1,4,7-triazacyclononane) and [Ru(bpy)(3)](3+)(bpy = 2,2'-bipyridine) were too fast to be followed by a conventional stopped-flow technique. Marcus cross relation for the outer-sphere electron transfer reaction was used to estimate the rate constants of the electron self-exchange reaction between Cu(II)-porphyrin and its pi-cation radical: log(k/M(-1) s(-1))= 9.5 +/- 0.5 for TPP and log(k/M(-1) s(-1))= 11.1 +/- 0.5 for OEP at 25.0 degrees C. Such large electron self-exchange rate constants are typical for the porphyrin-centered redox reactions for which very small inner- and outer-sphere reorganization energies are required.
authors.affiliation: Department of Chemistry, Aichi University of Education, Kariya 448-8542, Japan. minamo@auecc.aichi-edu.ac.jp
authors.forename: Masahiko
authors.initials: M
authors.lastname: Inamo
authors.forename: Hideto
authors.initials: H
authors.lastname: Kumagai
authors.forename: Ushio
authors.initials: U
authors.lastname: Harada
authors.forename: Sumitaka
authors.initials: S
authors.lastname: Itoh
authors.forename: Satoshi
authors.initials: S
authors.lastname: Iwatsuki
authors.forename: Koji
authors.initials: K
authors.lastname: Ishihara
authors.forename: Hideo D
authors.initials: HD
authors.lastname: Takagi
mesh_terms: D000097:Acetonitriles / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D008665:Metalloporphyrins / Q000737:chemistry*; D016877:Oxidants / Q000737:chemistry*
chemical_list: D000097:Acetonitriles; D008665:Metalloporphyrins; D016877:Oxidants; D003300:Copper; C032159:acetonitrile