We report herein a comprehensive study of (porphinato)iron [PFe]-catalyzed isobutane oxidation in which molecular oxygen is utilized as the sole oxidant; these catalytic reactions were carried out and monitored in both autoclave reactors and sapphire NMR tubes. In situ 19F and 13C NMR experiments, coupled with GC analyses and optical spectra obtained from the autoclave reactions have enabled the identification of the predominant porphyrinic species present during PFe-catalyzed oxidation of isobutane. Electron-deficient PFe catalysts based on 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin [(C6F5)4PH2], 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(pentafluorophenyl)porphyrin [Br8(C6F5)4PH2], and 5,10,15,20-tetrakis(heptafluoropropyl)porphyrin [(C3F7)4PH2] macrocycles were examined. The nature and distribution of hydrocarbon oxidation products show that an autoxidation reaction pathway dominates the reaction kinetics, consistent with a radical chain process. For each catalytic system examined, PFe(II) species were shown not to be stable under moderate O2 pressure at 80 °C; in every case, the PFe(II) catalyst precursor was converted quantitatively to high-spin PFe(III) complexes prior to the observation of any hydrocarbon oxidation products. Once catalytic isobutane oxidation is initiated, all reactions are marked by concomitant decomposition of the porphyrin-based catalyst. In situ 17O NMR spectroscopic studies confirm the incorporation of 17O from labeled water into the oxidation products, implicating the involvement of PFe-OH in the catalytic cycle. Importantly, Br8(C6F5)4PFe-based catalysts, which lack macrocycle C-H bonds, do not exhibit augmented stability with respect to analogous catalysts based on (C6F5)4PFe and (C3F7)4PFe species. The data presented are consistent with a hydrocarbon oxidation process in which PFe complexes play dual roles of radical chain initiator, and the species responsible for the catalytic decomposition of organic peroxides. This modified Haber-Weiss reaction scheme provides for the decomposition of tert-butyl hydroperoxide intermediates via reaction with PFe-OH complexes; the PFe(III) species responsible for hydroperoxide decomposition are regenerated by reaction of PFe(II) with dioxygen under these experimental conditions.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry