Display options
Cite
Maldotti A, Bartocci C, Varani G, et al. Oxidation of Cyclohexane by Molecular Oxygen Photoassisted by meso-Tetraarylporphyrin Iron(III)-Hydroxo Complexes. Inorg Chem. 1996;35(5):1126-1131doi: 10.1021/ic950386s.
Maldotti, A., Bartocci, C., Varani, G., Molinari, A., Battioni, P., & Mansuy, D. (1996). Oxidation of Cyclohexane by Molecular Oxygen Photoassisted by meso-Tetraarylporphyrin Iron(III)-Hydroxo Complexes. Inorganic chemistry, 35(5), 1126-1131. https://doi.org/10.1021/ic950386s
Maldotti, A., et al. "Oxidation of Cyclohexane by Molecular Oxygen Photoassisted by meso-Tetraarylporphyrin Iron(III)-Hydroxo Complexes." Inorganic chemistry vol. 35,5 (1996): 1126-1131. doi: https://doi.org/10.1021/ic950386s
Maldotti A, Bartocci C, Varani G, Molinari A, Battioni P, Mansuy D. Oxidation of Cyclohexane by Molecular Oxygen Photoassisted by meso-Tetraarylporphyrin Iron(III)-Hydroxo Complexes. Inorg Chem. 1996 Feb 28;35(5):1126-1131. doi: 10.1021/ic950386s. PMID: 11666299.
Copy Download .nbib Format: NLM
Share it on

Inorg Chem. 1996 Feb 28;35(5):1126-1131. doi: 10.1021/ic950386s.

Oxidation of Cyclohexane by Molecular Oxygen Photoassisted by meso-Tetraarylporphyrin Iron(III)-Hydroxo Complexes.

Inorganic chemistry

A. Maldotti, C. Bartocci, G. Varani, A. Molinari, P. Battioni, D. Mansuy

Affiliations

  1. Laboratoire de Chimie et Biochimie Pharmacologique Toxicologique, URA 400, Université René Descartes, 45 rue des Saints-Pères, 75270 Paris Cedex 06, France.

PMID: 11666299 DOI: 10.1021/ic950386s

Abstract

The photochemical and photocatalytic properties of iron meso-tetraarylporphyrins bearing an OH(-) axial ligand and different substituents in the beta-positions of the porphyrin ring are reported. Irradiation (lambda = 365 nm) in the absence of dioxygen leads to the reduction of Fe(III) to Fe(II) with the formation of OH(*) radicals. Substituents at the pyrrole beta-positions are found to markedly affect the photoreduction quantum yields. Under aerobic conditions, this photoreaction can induce the subsequent oxidation of cyclohexane to cyclohexanone and cyclohexanol by O(2) itself. The process occurs under mild conditions (22 degrees C; 760 Torr of O(2)) and without the consumption of a reducing agent. The polarity of the solvent and the nature of the porphyrin ring have a remarkable effect on the selectivity of the photooxidation process, likely controlling the cleavage of O-O bonds of possible iron peroxoalkyl intermediates. In particular, in pure cyclohexane, oxidation occurs with the selective formation of cyclohexanone; in contrast, in dichloromethane/cyclohexane mixed solvent, the main oxidation product is cyclohexanol. Phenyl-tert-butylnitrone (pbn) has been found to quench the radical chain autooxidation of the substrate thus increasing the yield of cyclohexanol. This becomes the only oxidation product when iron 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin hydroxide (Fe(III)(TDCPP)(OH)) is used as photocatalyst.

Publication Types