Abstract
The bromide anation of tr-PtCl 4BrH 2O − has been studied at 25°C and the chloride anations of tr-PtCl 4BrH 2O − and PtBr 5H 2O − at 50°C. These reactions proceed via halide assisted mechanisms, compatible with the experimental rate laws: ▪ The bromide anation of tr-PtBr 4CIH 2O − studied at 50°C gives PtBr 5Cl 2− via a bromide assisted path andPtBr 2− 6 via an REOA-path. The observed rate law is ▪ PtBr 5Cl 2− reacts subsequently with bromide to form PtBr 2− 6 via a rate-determining (bromide assisted or REOA) formation of an intermediate aqua complex according to the mechanism ▪ The observed rate law at 50°C is ▪ All reactions have been studied in a 0.50 M perchloric acid medium. A general survey of reactivity correlations and mechanisms for platinum(IV) anation reactions is given. Effects of reductants, bridging and entering ligands, and of the four non-labile ligands in the plane around the platinum atom are quantitatively compared.
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