Competitive Oxidation and Protonation of Aqueous Monomethylplatinum(II) Complexes: A Comparison of Oxidants
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Abstract
[PtII(CH3)Cl3]2- (1), generated at 95 °C in situ from Cs2[PtIV(CH3)2Cl4] in an aqueous solution of high chloride concentration and [H+] = 0.2 M, undergoes competitive oxidation versus protonation (kox/kH+) with several oxidants. A first-order dependence on oxidant concentration was determined for both CuCl2 and FeCl3 oxidations of 1, and kox/kH+ was determined to be 191 ± 24 and 14 ± 3. CuCl2 was shown to catalyze the oxidation of 1 by dioxygen; however, [PtIICl4]2- was also oxidized under these conditions. Anion 1, generated in a mixture of platinum(II) salts, [Cp2CoIII]2{[PtIICl4] + 1 + [PtII(CH3)2Cl2] (4)}·xNaCl (5), also undergoes competitive oxidation and protonation at room temperature in D2O when in the presence of oxidants. Increasing chloride decreases the ratio kox/kH+ for 1 when Na2[PtIVCl6] is used as the oxidant, but when CuCl2 is used as the oxidant, added chloride increases kox/kH+. The one-electron oxidants, Na2[IrCl6] and (NH4)2[Ce(NO3)6], were also shown to oxidize 1.
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