Mechanistic Studies on the Hexadecafluorophthalocyanine-iron-Catalyzed Wacker-type Oxidation of Olefins to Ketones.

The hexadecafluorophthalocyanine-iron complex FePcF16 was recently shown to convert olefins into ketones in the presence of stoichiometric amounts of triethylsilane in ethanol at room temperature under an oxygen atmosphere. Herein, we describe an extensive mechanistic investigation for the conversion of 2-vinylnaphthalene into 2-acetylnaphthalene as model reaction. A variety of studies including deuterium- and 18O2-labeling experiments, ESI-MS, and 57Fe Mossbauer spectroscopy have been performed to identify the intermediates involved in the catalytic cycle of the oxidation process. Finally, a detailed and well-supported reaction mechanism for the FePcF16-catalyzed Wacker-type oxidation has been proposed.