Abstract
The kinetics of oxidation of ascorbic acid and a series of substituted 1,2- and 1,4-dihydroxybenzene compounds (H2Q) by [Ru(CN)6]3– have been investigated in acidic perchlorate media. The inverse dependences of the rate constants on acid concentrations for 2,3-dicyano-1,4-dihydroxybenzene, 4,5-dihydroxybenzene-1,3-disulphonate, and ascorbic acid have been attributed to concurrent rate-determining pathways involving the one-electron oxidations of H2Q or HQ– by [Ru(CN)6]3– to the corresponding semiquinone or ascorbate radical intermediate. The cross-reaction rate constants have been correlated with the semiquinone or ascorbate reduction potentials in terms of the Marcus relationship to yield a [Ru(CN)6]3––[Ru(CN)6]4– electron self-exchange rate constant of (1.0 ± 0.8)× 105 dm3 mol–1 s–1. This is compared with those for other low-spin d5–d6 transition-metal complex couples and discussed in terms of the inner-sphere and solvent reorganization energies.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callMore From: Journal of the Chemical Society, Dalton Transactions
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
