Metalloporphyrin-catalyzed homogeneous oxidation in supercritical carbon dioxide

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

Research output: Contribution to journalArticle

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 languageEnglish
Pages (from-to)11-24
Number of pages14
JournalJournal of Molecular Catalysis A: Chemical
Volume139
Issue number1
DOIs
Publication statusPublished - 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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