Relative electron-donating ability of simple alcohol radicals toward 12-heteropolytungstates. A pulse radiolysis study

Abstract

The pulse-radiolysis technique has been used to study the reaction of one-electron reducing radicals [CH₂OH, CH₃ĊHOH and (CH₃)₂ĊOH] with a series of heteropolytungstates, [PW₁₂O₄₀]^3–, [SiW₁₂O₄₀]^4–, [FeW₁₂O₄₀]^5– and [H₂W₁₂O₄₀]^6–, to produce the corresponding one-electron reduction products.

A gradual decrease in rate constants with (a) increasing negative charge and (b) increasing negative reduction potentials of the heteropolyanions is observed. The relative reaction rates increasing negative reduction potentials of the heteropolyanions is observed. The relative reaction rates increase in the sequence ĊH₂OH < CH₃ĊHOH < (CH₃)₂ĊOH, which is the same order as that of their electron donating abilities.