Accession Number:

ADA334890

Title:

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

Descriptive Note:

Final rept.

Corporate Author:

AIR FORCE RESEARCH LAB BOLLING AFB DC

Personal Author(s):

Report Date:

1995-01-01

Pagination or Media Count:

365.0

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 pentafluorophenylporphyrinato-rutheniumII carbonyl RuTFPPCl8CO and beta -octabromo-tetrakispentafluorophenylporphyrinato- ironIII chloride FeTFPPBr8Cl are reported. Crystal structures of RuTFPPCl8CO 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.

Subject Categories:

  • Organic Chemistry

Distribution Statement:

APPROVED FOR PUBLIC RELEASE