Metalloporphyrin-catalyzed homogeneous oxidation in supercritical carbon dioxide

Eva R. Birnbaum; Richard M. Le Lacheur; April C. Horton; William Tumas

doi:10.1016/S1381-1169(98)00172-1

Metalloporphyrin-catalyzed homogeneous oxidation in supercritical carbon dioxide

Eva R. Birnbaum, Richard M. Le Lacheur, April C. Horton, William Tumas

National Renewable Energy Laboratory

Research output: Contribution to journal › Article › peer-review

67 Citations (Scopus)

Abstract

We report results from a study of the reactivity of the halogenated porphyrins tetrakis(pentafluorophenyl)porphyrinato iron(III) chloride [Fe(TFPP)Cl] and β-octabromo-tetrakis(pentafluorophenyl)porphyrinato iron(III) chloride [Fe(TFPPBr₈)Cl] with dioxygen and cyclohexene in supercritical carbon dioxide. A lower limit for the solubility of the iron porphyrins in sc CO₂ was determined. Both halogenated metalloporphyrins were active catalysts for oxidation of cyclohexene to epoxide and allylic oxidation products in sc CO₂. In 12 h at 80°C, up to 350 and 580 turnovers were observed for Fe(TFPP)Cl and Fe(TFPPBr₈)Cl, respectively. We have also explored several organic solvent reactions at high temperature and pressure to benchmark relative activity and selectivity. Activity is higher in organic solvent, but accompanied by substantial oxidation of, or reaction with the solvent. Selectivity for epoxidation with Fe(TFPPBr₈)Cl is higher in sc CO₂ than in organic solvents, with up to 34% cyclohexene oxide produced.

Original language	English
Pages (from-to)	11-24
Number of pages	14
Journal	Journal of Molecular Catalysis A: Chemical
Volume	139
Issue number	1
DOIs	https://doi.org/10.1016/S1381-1169(98)00172-1
Publication status	Published - Feb 19 1999

Keywords

Metallophorphyrins
Oxidation
Supercritical carbon dioxide

ASJC Scopus subject areas

Catalysis
Process Chemistry and Technology
Physical and Theoretical Chemistry

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abstract = "We report results from a study of the reactivity of the halogenated porphyrins tetrakis(pentafluorophenyl)porphyrinato iron(III) chloride [Fe(TFPP)Cl] and β-octabromo-tetrakis(pentafluorophenyl)porphyrinato iron(III) chloride [Fe(TFPPBr8)Cl] with dioxygen and cyclohexene in supercritical carbon dioxide. A lower limit for the solubility of the iron porphyrins in sc CO2 was determined. Both halogenated metalloporphyrins were active catalysts for oxidation of cyclohexene to epoxide and allylic oxidation products in sc CO2. In 12 h at 80°C, up to 350 and 580 turnovers were observed for Fe(TFPP)Cl and Fe(TFPPBr8)Cl, respectively. We have also explored several organic solvent reactions at high temperature and pressure to benchmark relative activity and selectivity. Activity is higher in organic solvent, but accompanied by substantial oxidation of, or reaction with the solvent. Selectivity for epoxidation with Fe(TFPPBr8)Cl is higher in sc CO2 than in organic solvents, with up to 34% cyclohexene oxide produced.",

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AU - Birnbaum, Eva R.

AU - Le Lacheur, Richard M.

AU - Horton, April C.

AU - Tumas, William

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AB - We report results from a study of the reactivity of the halogenated porphyrins tetrakis(pentafluorophenyl)porphyrinato iron(III) chloride [Fe(TFPP)Cl] and β-octabromo-tetrakis(pentafluorophenyl)porphyrinato iron(III) chloride [Fe(TFPPBr8)Cl] with dioxygen and cyclohexene in supercritical carbon dioxide. A lower limit for the solubility of the iron porphyrins in sc CO2 was determined. Both halogenated metalloporphyrins were active catalysts for oxidation of cyclohexene to epoxide and allylic oxidation products in sc CO2. In 12 h at 80°C, up to 350 and 580 turnovers were observed for Fe(TFPP)Cl and Fe(TFPPBr8)Cl, respectively. We have also explored several organic solvent reactions at high temperature and pressure to benchmark relative activity and selectivity. Activity is higher in organic solvent, but accompanied by substantial oxidation of, or reaction with the solvent. Selectivity for epoxidation with Fe(TFPPBr8)Cl is higher in sc CO2 than in organic solvents, with up to 34% cyclohexene oxide produced.

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KW - Oxidation

KW - Supercritical carbon dioxide

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