Abstract
Pentafluoroiodosylbenzene (C6F5IO) selectively oxidizes Pd−C bonds of a series of cyclopalladated 2-(alkylthio)azobenzene complexes. The kinetics of oxygen atom insertion into the Pd−C bond of one representative compound has been studied in detail to understand the mechanism of this reaction. At 20 °C Pd−C bond oxidation takes place smoothly in acetonitrile at a rate of 0.08 M-1 s-1, whereas this reaction does not proceed in solvents such as dichloromethane and chloroform. The ΔH⧧ and ΔS⧧ values for this reaction are 55.5 ± 3.5 kJ/mol and −75.7 ± 11.5 eu, respectively. Among other oxidants, hydroperoxy radical (for example, t-BuOO•) is found to be extremely efficient, whereas the highly electrophilic oxoiron(IV) porphyrin cation radical (oxene) is incapable of oxidizing the Pd−C bond. Oxene, however, selectively oxidizes the thioether functionality. These observations suggest that nucleophilic attack of the oxidant molecule on palladium(II) could be the most crucial step prior to Pd−C bond oxidation. A la...
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