Synthesis and Electrochemistry of Iron(III) Corroles Containing a Nitrosyl Axial Ligand. Spectral Characterization of [(OEC)FeIII(NO)]n where n = 0, 1, 2, or -1 and OEC is the Trianion of 2,3,7,8,12,13,17,18-Octaethylcorrole

High-valent transition metal corrolazines

“…Oxidation of Co(OEC)(Ph) to Co(OEC)(Ph) + has the effect of decreasing mean-plane-separation by 0.05 Å and lateral shift by 2.01 Å . Similar parameters were also observed for the Fe III p-cation radical complex Fe(OEC)(NO) + [76]. Comparison of the geometric parameters in Table 5 seems to suggest that the corrolazine ring in 6 maintains a closedshell configuration, implying a Co IV oxidation state.…”

Iron corrolates: Unambiguous chloroiron(III) (corrolate)2− π-cation radicals

“…The first report of electrochemical investigation of iron corrolates was in 1994 by Vogel, Kadish and co-workers [93]. In this work the synthesis, structural and spectral characterization of [Fe(NO)(OECorr)] and [Fe(NO)(OECorr)] + were reported.…”

“…The singly-oxidized form of this complex, [Fe(NO)(OECorr)] + , also exhibits an EPR spectrum, rhombic in shape, with g = 2.02, 2.00, and 1.98 [93]. Although it was concluded that this EPR spectrum is consistent with low-spin Fe(III), Fe(III)-NO complexes are EPR silent [96] (as is the starting material, [Fe(NO)(OECorr)]), and analysis as a low-spin Fe(III) complex yields totally unreasonable crystal field parameters [91] (V/k = 50.5, D/k = À 48.25, V/D = À 1.05).…”

“…Thus, for both reasons, as well as the lack of 14 N superhyperfine structure on the EPR signal, it is likely that this is the EPR signal of the p-cation radical of the corrolate. In fact, the authors know that the complex [Fe(NO)(OECorr)] + contains a p-cation radical, because the X-ray crystallographic characterization of this oxidized complex shows that the two corrole planes are very close to each other (3.21 Å ) [93] that appears to allow spin coupling between the two macrocycle radicals similar to what has been observed previously for octaethylporphyrin-metal pcation radicals [90,97,98]. This implies that the singly-oxidized corrole is best formulated as an iron(III) p-cation radical rather than an iron(IV) nitrosyl.…”

Investigation of the electrochemical behavior of metallo-tetraazaporphyrin modified silver and pyrolytic graphite electrodes in aqueous nitrite solution

“…Meyer and co-workers [11] observed that water-soluble iron(III) porphyrins catalyze reduction of nitrites in acidic medium to a mixture of products. This involved a nitrosyl complex intermediate [12,13]. Cobalt(II) porphyrins also catalyze reduction of nitrite in homogeneous solutions [14][15][16].…”