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Published January 1, 2007 | Supplemental Material
Journal Article Open

Competitive Oxidation and Protonation of Aqueous Monomethylplatinum(II) Complexes: A Comparison of Oxidants


[Pt^(II)(CH_3)Cl_3]^(2-) (1), generated at 95 °C in situ from Cs_2[Pt^(IV)(CH_3)_2Cl_4] in an aqueous solution of high chloride concentration and [H^+] = 0.2 M, undergoes competitive oxidation versus protonation (k_(ox)/k_(H+)) with several oxidants. A first-order dependence on oxidant concentration was determined for both CuCl_2 and FeCl_3 oxidations of 1, and k_(ox)/k_(H+) was determined to be 191 ± 24 and 14 ± 3. CuCl_2 was shown to catalyze the oxidation of 1 by dioxygen; however, [Pt^(II)Cl_4]^(2-) was also oxidized under these conditions. Anion 1, generated in a mixture of platinum(II) salts, [Cp_2Co^(III)]_2{[Pt^(II)Cl_4] + 1 + [Pt^(II)(CH_3)_2Cl_2] (4)}·xNaCl (5), also undergoes competitive oxidation and protonation at room temperature in D_2O when in the presence of oxidants. Increasing chloride decreases the ratio k_(ox)/k_(H+) for 1 when Na_2[Pt^(IV)Cl_6] is used as the oxidant, but when CuCl_2 is used as the oxidant, added chloride increases k_(ox)/k_(H+). The one-electron oxidants, Na_2[IrCl_6] and (NH_4)_2[Ce(NO_3)_6], were also shown to oxidize 1.

Additional Information

© 2007 American Chemical Society. Received 22 August 2006. Published online 24 November 2006. Published in print 1 January 2007. We thank Larry Henling for identifying the Cs_2[Pt^(IV)Cl_6] crystals using X-ray crystallography, and we are grateful to bp for financial support through the MC2 program.

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