Preparation, solution properties, and structure of iron(III) porphyrin oxyanion complexes. Crystal and molecular stereochemistry of a novel bidentate nitrato complex

Mechanistic studies of nitrite reactions with metalloproteins and models relevant to mammalian physiology

“…(28)). The nitrato complex had previously been characterized by X-ray crystallography as having an asymmetrically bound nitrate ligand [131],…”

FTIR and optical spectroscopic studies of the reactions of heme models with nitric oxide and other NOx in porous layered solids

“…According to structural data the nitrato ligand of Fe III (TPP)( 2 -O 2 NO) is bidentate [71], and the Fe(III) is in the high-spin state with a large out-of-plane displacement (0.6Å) toward the coordinated nitrate. The energy difference between bidentate and monodentate coordination must be small given that the octaethylporphyrinato analog Fe III (OEP)( 1 -ONO 2 ) is monodentate [72], and this view is supported by DFT computations with the porphinato complex Fe(P)(NO 3 ).…”

Electrochemistry and spectroscopy of sulfate and thiosulfate complexes of iron porphyrins

“…In both DMF-d7 and DMSO-d6/toluene-d8 (at 0C), the proton NMR spectra in the presence and absence of thiosulfate are consistent with a high-spin ferric complex [17,18], though small changes in the chemical shifts were observed when thiosulfate was present. For example, the pyrrole resonance of Fe(TPP)(Cl) in DMF-d7 was shifted from 82.5 ppm to 77.0 ppm when thiosulfate was added.…”

“…The supporting electrolyte, tetrabutylammonium perchlorate (TBAP), was obtained from G. F. Smith Chemical Co., and was used as received. Sodium thiosulfate was obtained from Fisher Scientific Co. Tetraphenylporphyrinato iron(III) chloride (Fe(TPP)(Cl)) [28] and [Fe(TPP)]2(SO4) [18] were synthesized by literature procedures.…”

“…The first report from this laboratory has been published [17]. Dianions such as sulfate were found to form dimeric ferric porphyrin complexes in non-coordinating solvents such as methylene chloride [17][18][19][20]. Three reduction waves were observed in cyclic voltammetry due to the reduction of the dimer, the sulfate complex, and the ferrous porphyrin.…”