The kinetics and stoicheiometry of silver(III) reduction by the octacyano-complexes of molybdenum(IV) and tungsten(IV)
Document Type
Article
Date of Original Version
12-1-1985
Abstract
The reactions of [Ag(OH)4]- with [Mo(CN)8]4- and [W(CN)8]4- involve an initial one-electron reduction of AgIII to AgII with second-order rate constants of 80 and 2.9 × 104 dm3 mol-1 s-1 (25 °C, I = 1.2 mol dm-3), respectively. The tungstate reaction is quantitative with a stoicheiometry of 1:1. The reaction with [Mo(CN)8]4-, however, does not go to completion. There is apparently an equilibrium of oxidation states. From the value of the equilibrium constant a formal potential of 0.87 V ([OH-] = 1.2 mol dm-3, 25 °C) is estimated for the reduction of [Ag(OH)4]- to dimeric AgII. The rate of the initial one-electron redox step is strongly correlated with EM/M+ for the series of reductants [Fe(CN)6]4-, MnO42-, [W(CN)8]4-, and [Mo(CN)8]4-. The results are interpreted in terms of a general mechanism which involves silver(II) polymerisation following the initial redox step.
Publication Title, e.g., Journal
Journal of the Chemical Society, Dalton Transactions
Issue
9
Citation/Publisher Attribution
Borish, Edward T., Louis J. Kirschenbaum, and Edoardo Mentasti. "The kinetics and stoicheiometry of silver(III) reduction by the octacyano-complexes of molybdenum(IV) and tungsten(IV)." Journal of the Chemical Society, Dalton Transactions 9 (1985). doi: 10.1039/DT9850001789.