Kinetics of Electron Transfer from Cyclic Ketones to Ni(IV) Periodate Complex in Aqueous Alkaline Medium

Article abstract of DOI:10.1246/bcsj.62.1300

The kinetics of electron transfer from cyclic ketones (represented by (S)) to Ni(IV) periodate complexes has been studied in aqueous alkaline medium.The kinetics exhibit a pseudo-first-order disappearance of Ni(IV) periodate complexes when the is present in excess.The pseudo-first-order rate constants k_obs, were linearly dependent on and the order is were found to be unity.The rate of the reaction increased with the increase in ->, however the rates were retarded with the increase in .Salt and solvent effect studies indicate that the reaction is of ion-dipole type.A suitable mechanism involving slow adduct formation between anol and oxidant, and its decomposition in a fast step have been suggested.A rate law consistent with the proposed mechanism has also been derived.The products of oxidation were identified as corresponding decarboxylic acids.