| The objective of this work is to build a “Molecular level reactor” in which the metal center is the catalyst while the building cavity surrounding it imitates a robust, Teflon coated reactor wall. The metal complexes should be suitable for performing selective activation of molecular oxygen. The major practical application is the effective utilization of natural resources. Air was used to selectively derivatize hydrocarbons, especially cyclohexane and methane, which is ultimate goal of hydrocarbons oxidation chemistry.; The synthetic targets are three dimensional perfluorinated phthalocyanines. These metal phthalocyanines contain Ru, Fe, and Co as the metal center, reminiscent of the architecture of Cytochrome P-450.; The selective oxidation of hydrocarbon under mild conditions is one of the most challenging problems in chemistry, yet the number of reported methods for the selective, low temperature oxidation of hydrocarbon is limited. Porphyrin and phthalocyanine including halogenated complexes have limited stability as a catalyst during oxidations because of the susceptibility of aromatic halogen to nucleophilic attack. Planar of porphyrin and phthalocyanines can also easily form inert μ-oxo dimerized complexes. The three dimensional perfluoro isopropyl phthalocyanines reported here contains no carbon-hydrogen bonds, only thermodynamically strong carbon-fluorine bonds preventing self destruction during the oxidation reaction. Their steric bulkiness favors single-site isolation, i.e. disfavors dinuclear complexes.; In this research, F64PcM, M = H2, Co, Fe, and Ru, were prepared and fully characterized. Cyclohexane, and preliminarily methane oxidation were performed with F64PcFe and F64PcRu(CO) complexes in homogeneous systems. F64PcCo was catalyzes the oxidative formation of carbon—phosphorous double bonds. The oxidation and oxygenation of C-H bonds with the molecular Teflon-coated reactor demonstrated the judicious ligand design strategy and provide opportunities for “Green Chemistry” processes. |
