title: Kinetic studies of the reduction of [Co(dmgH)2(py)(Cl)] revisited: mechanisms, products, and implications.
abstract: We report on a mechanistic investigation regarding the reduction of [Co(III)(dmgH)2(py)(Cl)] (dmg = dimethylglyoxime) by several complementary techniques. The reduction of [Co(III)(dmgH)2(py)(Cl)] was initiated by either electrochemical, photochemical, or pulse radiolytical techniques, and the corresponding products were analyzed by ESI mass spectrometry. In addition, all of the rate constants for each step were determined. We have found solid experimental as well as theoretical evidence for the appearance of a dinuclear complex [Co(II)Co(III)(dmgH)4(py)2(H2O)2](+) to be the final product of reduction, implying the initially reduced form of [Co(III)(dmgH)2(py)(Cl)] undergoes a dimerization with the starting material in solution.
authors.affiliation: Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU) , Egerlandstr. 3, 91058 Erlangen, Germany.
authors.forename: Axel
authors.initials: A
authors.lastname: Kahnt
authors.forename: Katrin
authors.initials: K
authors.lastname: Peuntinger
authors.forename: Claudia
authors.initials: C
authors.lastname: Dammann
authors.forename: Thomas
authors.initials: T
authors.lastname: Drewello
authors.forename: Ralf
authors.initials: R
authors.lastname: Hermann
authors.forename: Sergej
authors.initials: S
authors.lastname: Naumov
authors.forename: Bernd
authors.initials: B
authors.lastname: Abel
authors.forename: Dirk M
authors.initials: DM
authors.lastname: Guldi