Oxidation of organic compounds by silver(II). Reactions with aliphatic diols and α-hydroxy acids
Date of Original Version
The rate of oxidation by silver(II) of succinic, malic, tartaric, glycolic and lactic acids and 1,2- ethanediol, 1,2-propanediol, 1,3-propanediol, and 1,2-ethanediol monomethyl ether has been investigated in acidic perchlorate media by the stopped-flow technique. For all substrates (S) except 1,2-ethanediol and 1,3-propanediol reactions were first order in total silver and in S with an observed rate constant kobs=2(k1 + k2Kh[H+]-1) reflecting parallel oxidations by aquasilver(II)(k1) and AgOH+ (k2). In the case of 1,2-ethanediol and 1,3-propanediol, plots of the pseudo first order rate constant kobs versus [S] showed a levelling off behavior which is indicative of an association process prior to redox. The proposed mechanism involves formation of a Ag(I)-diol complex, rapidly oxidized by aquasilver(II) to Ag(II)-diol, which, in turn, undergoes redox decomposition. Stoichiometry, nature of the intermediate species, and reactivity patterns are discussed. © 1987.
Publication Title, e.g., Journal
Inorganica Chimica Acta
Mentasti, Edoardo, and Louis J. Kirschenbaum. "Oxidation of organic compounds by silver(II). Reactions with aliphatic diols and α-hydroxy acids." Inorganica Chimica Acta 134, 2 (1987). doi: 10.1016/S0020-1693(00)88097-4.