Mechanistic Studies on the Hexadecafluorophthalocyanine-Iron-Catalyzed Wacker-Type Oxidation of Olefins to Ketones*

Abstract

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 ¹⁸ O₂ -labeling experiments, ESI-MS, and ⁵⁷ Fe Mössbauer spectroscopy were 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 is proposed.

Keywords: Mössbauer spectroscopy; iron; labeling studies; oxidation; reaction mechanism.