A Stable Hyponitrite-Bridged Iron Porphyrin Complex

The coupling of two nitric oxide (NO) molecules in heme active sites is an important contributor to the conversion of NO to nitrous oxide (N2O) by heme-containing enzymes. Several formulations for the presumed heme-Fe{N2O2}(n+) intermediates have been proposed previously, however, no crystal structures of heme-Fe{N2O2}(n+), systems have been reported to date. We report the first isolation and characterization of a stable bimetallic hyponitrite iron porphyrin, [(OEP)Fe](2)(mu-N2O2), prepared from the reaction of [(OEP)Fe](2)(mu-O) with hyponitrous acid. Density functional theoretical calculations were performed on the model compound [(porphine)Fe](2)(mu-N2O2) to characterize its electronic structure and properties.