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Complex Formation followed by Internal Electron Transfer: the Reaction of silver(III) with Ascorbic Acid

DOI: 10.1039/DT9930000567

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 567 - 570 (1993)

Update date:2022-08-17

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Authors:

Dasgupta, SubrataDasgupta, Subrata

Herlinger, ErwinHerlinger, Erwin

Linert, WolfgangLinert, Wolfgang

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Article abstract of DOI:10.1039/DT9930000567

silver(III) 3+ 1 has been found to oxidize ascorbic acid (H2asc) in acidic aqueous solution via an inner-sphere mechanism to give dehydroascorbic acid, silver(I) and free ethylenebis(biguanide).The 1:1 adduct formed as an intermediate between 1 and ascorbic acid decomposes after a non-separable two-electron-transfer reaction.The decomposition of the three complexes actually formed, co-ordinating different numbers of protons, occurs through two parallel pathways: one via decomposition of the unprotonated adduct III(H2L)(H2asc)>, another via the deprotonated adduct III(H2L)(Hasc)>, while the protonated adduct III(H3L)(H2asc)> appears to be rather stable.The equilibrium constant for the adduct formation has been found to be 4.08 +/- 0.45 dm3 mol-1, whereas the acid and base constants of this complex are 0.41 mol dm-3 and 2.86 dm3 mol-1, respectively.The two rate constants for the decomposition are 25 +/- 3 and 220 +/- 25 s-1 for III(H2L)(H2asc)> and III(H2L)(Hasc)>, respectively.The possibility of an outer-sphere mechanism is discussed.

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