The Mechanism of Catalytic Hydrocarbon Oxidation by Molecular Oxygen and Halogenated Ruthenium and Iron Porphyrins

Abstract

Highly halogenated ruthenium and iron porphyrins are shown to be active catalysts for alkene oxidation with dioxygen or iodosobenzene. The synthesis and characterization of beta-octachloro-tetrakis (pentafluorophenyl)porphyrinato-ruthenium(II) carbonyl RuTFPPCl8(CO) and beta -octabromo-tetrakis(pentafluorophenyl)porphyrinato- iron(III) chloride Fe(TFPPBr8)Cl are reported. Crystal structures of RuTFPPCl8(CO) and the zinc and free ligand precursor complexes show extensive distortion of the halogenated porphyrin macrocycles due to steric interactions between the beta-chlorine atoms and the pentafluorophenyl rings. 19F NMR is developed as a method to characterize both paramagnetic and diamagnetic fluorinated porphyrins in solution. The anodically shifted reduction potentials and red shifted absorptions in the UV-Vis spectroscopy of the halogenated porphyrins are discussed in terms of steric and electronic effects on porphyrin frontier orbitals.

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Document Details

Document Type
Technical Report
Publication Date
Jan 01, 1995
Accession Number
ADA334890

Entities

People

  • Eva R. Birnbaum

Organizations

  • Air Force Research Laboratory

Tags

Communities of Interest

  • Advanced Electronics
  • C4I
  • Energy and Power Technologies
  • Ground and Sea Platforms

DTIC Thesaurus Topics

  • Alkanes
  • Alkenes
  • Carbonyl Complexes
  • Chemical Reaction Properties
  • Chemical Reactions
  • Chemical Synthesis
  • Chemistry
  • Energy Bands
  • Liquid Chromatography
  • Organic Chemistry
  • Oxidation
  • Spectroscopy
  • Visible Spectra

Fields of Study

  • Chemistry

Readers

  • Organic Chemistry
  • Quantum Chemistry

Technology Areas

  • Microelectronics
  • Space