Abstract
Rate constants are reported for the reaction of [PtCl4]2− with hydrochloric-perchloric acid mixtures, in aqueous methanol and aqueous t-butanol at 308.2 K. The observed first-order rate constants are, from their dependence on chloride concentration, divisible into forward and reverse rate constants for the equilibrium: [PtCl14]2−+H2O⇌[PtCl3(OH2)]−+Cl−. The solvent dependence of aquation rates for [PtCl4]2− is compared with those for other chlorotransition metal complexes, and discussed in terms of the Grunwald-Winstein method of mechanism diagnosis in organic systems. The solvent dependence of rates of [PtCl4]2− formation is compared with the rates of formation of other metal complexes; differences between this platinum reaction and, for example, nickel(II) formation, are rationalised in terms of the reactant charge product difference and consequent solvent permittivity effects on rate trends.
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