Synthesis of μ-Oxo-bisiron(III)Porphyrin Compounds and Their Catalysis for Cyclohexane Hydroxylation

• Published in: Journal of catalysis Vol. 178; no. 1; pp. 182 - 187
• Main Author: Guo, Can-Cheng
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier Inc 15.08.1998; Elsevier
• Subjects: Catalysis; Catalysts: preparations and properties; Chemistry; Exact sciences and technology; General and physical chemistry; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; oxidation; porphyrin; catalyze; Substituent effect; Ligand effect; Hydrocarbon; Hydroxylation; Molecular structure; Organic ligand; Transition metal Complexes; Experimental study; Synthesis; Iron III Complexes; Cyclohexane; Reagents; Metalloporphyrin; Catalyst; Organic compounds
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1006/jcat.1998.2138

Fourteen substituted μ-oxo-bis[tetraphenylporphinatoiron(III)] derivants ([TXPPFeIII]2O) were synthesized by passing chlorotetraphenylporphinatoiron(III) (TPPFeIIICl) through a neutral alumina chromatographic column, and nine of which were used in cyclohexane hydroxylation with PhIO as a new type of catalyst under moderate conditions. The experiments have shown that the yields, rate constantskof the cyclohexane hydroxylation have a linear relationship to characteristic constants σ of substituents on porphyrin rings, a physical constant characterizing the electronic effects and steric effects of a substituent group, and that the product distributions and kinetic properties of the reactions are dependent on the reaction temperature, solvent as well as air. In contrast with monoironporphyrin TPPFeIIICl, μ-oxo-bisironporphyrin [TPPFeIII]2O is shown to have the better catalytic power for cyclohexane hydroxylation with PhIO under moderate conditions and stability to PhIO. The research results show that μ-oxo-bisironporphyrin can be used as the model compound of cytochrome P-450 monooxygenase.