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High-valent copper(ii) porphyrins and oxy-ligated metalloporphyrins

Thesis/Dissertation ·
OSTI ID:5347175

Results from four related projects are presented. First, a base-catalyzed deuterium exchange procedure for the ring adjacent methyl and methylene protons of porphyrins and metalloporphyrins is reported. In 24 hours nearly quantitative ring methylene deuteration is achieved, but significant porphyrin degradation is noted. Several copper (II) and silver (II) porphyrins and their one-electron oxidation products were examined by NMR spectroscopy. A novel manganese (III) porphyrin dimeric compound has been synthesized and structurally characterized by electronic and magnetic resonance spectroscopy. Metal derivatives of 5-(2-hydroxyphenyl)-10, 15, 20-tritolylporphyrin dimerize through the formation of phenolato bridges. Several new oxyanion complexes of iron (III) tetraphenylporphyrin have been prepared. The iron (III) porphyrin complexes of chromate, iodate and perrhenate have been synthesized. Electronic, NMR and EPR spectra of these species confirm the retention of a high-spin iron (III) configuration.

Research Organization:
Iowa Univ., Iowa City (USA)
OSTI ID:
5347175
Country of Publication:
United States
Language:
English