Low Reorganization Energy for Electron Self-Exchange by a Formally Copper(III,II) Redox Couple.

ABSTRACT: The rate constant for electron self-exchange (k₁₁) between LCuOH and [LCuOH]^- (L = bis-2,6-(2,6-diisopropylphenyl)carboximidopyridine) was determined using the Marcus cross relation. This work involved measurement of the rate of the cross-reaction between [Bu₄N][LCuOH] and [Fc][BAr₄^F] (Fc⁺ = ferrocenium; BAr₄^F = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate)) by stopped-flow methods at -88 °C in CH₂Cl₂ and measurement of the equilibrium constant for the redox process by UV-vis titrations under the same conditions. A value of k₁₁ = 3 × 10⁴ M^-1 s^-1 (-88 °C) led to estimation of a value 9 × 10⁶ M^-1 s

SUBMITTER: Zerk TJ 

PROVIDER: S-EPMC7200075 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature