The tendency of olefins to chemisorb irreversibly on platinum electrodes is exploited to attach a variety of reactive entities to the electrode surface. Chelates connected to the electrode surface through an olefinic side chain allow metals to be selectively chemisorbed at the electrode surface. The stability of the chemisorbed metal complex is shown to vary with electrode potential, due to the influence of the electrical double layer, in such a way that the chelating ability of the chemisorbed chelate can effectively be "switched" on or off. Studies of the electrode reactions of chemisorbed complexes of Fe and Pt and of organic depolarizers such as substituted polyhydric phenols indicate that only in certain instances are the adsorbed reactants able to achieve a reactive orientation of the sort acquired readily by dissolved species. Evidence is presented that the system of each adsorbed olefin studied undergoes ten-electron oxidation to form the corresponding carboxylic acid and/or CO2. Equations which describe the electrochemistry of chemisorbed molecules are derived and tested.
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