Platinum chemical wave formation

Chemical and electrochemical oxidation of these [Pt Me2(a-diimine)] species in MeCN was later studied in more detail in the Tdset group (38). Irreversible electrochemical waves were again observed, and bulk electrolysis revealed consumption of 1.1-1.6 FmoP indicative of a le oxidation process. (Electro)chemical bulk oxidation leads to only marginal formation of methane or ethane, and almost quantitative formation of the species [Pt Me3(a-diimine)(NCMe)] and [Pt Me(a-diimine)(NCMe)] in a 1 1 ratio. It was proposed that the short-lived [Pt Me2(a-diimine)] " " decomposes via a bimolecular methyl transfer from one platinum to another. This explains the product distribution and the lack of products derived from free alkyl radicals. This could either involve a reaction between two [Pt °Me2(a-diimine)] + intermediates or a reaction of [Pt° Me2(a-diimine)] + with the starting material [Pt Me2 (a-diimine)]. 

Platinum/ platinum family metals/ and silver are classified in the second group. The oxygen electroreduction on these metals occurs both directly to water and via intermediate formation of hydrogen peroxide. The hydrogen peroxide formed in the parallel reaction is decomposed by chemical or electrochemical mechanisms. The relation between the rates of these processes depends in a complicated way on the nature of the metal, the potential, the coverage of the electrode by the chemisorbed species, and their adsorption character. The polarization curves are characterized by a single wave with a limiting current close to the diffusion current for the four-electron process. 

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