title: β-Nitro derivatives of iron corrolates.
abstract: Two different methods for the regioselective nitration of different meso-triarylcorroles leading to the corresponding β-substituted nitrocorrole iron complexes have been developed. A two-step procedure affords three Fe(III) nitrosyl products-the unsubstituted corrole, the 3-nitrocorrole, and the 3,17-dinitrocorrole. In contrast, a one-pot synthetic approach drives the reaction almost exclusively to formation of the iron nitrosyl 3,17-dinitrocorrole. Electron-releasing substituents on the meso-aryl groups of the triarylcorroles induce higher yields and longer reaction times than what is observed for the synthesis of similar triarylcorroles with electron-withdrawing functionalities, and these results can be confidently attributed to the facile formation and stabilization of an intermediate iron corrole π-cation radical. Electron-withdrawing substituents on the meso-aryl groups of triarylcorrole also seem to labilize the axial nitrosyl group which, in the case of the pentafluorophenylcorrole derivative, results in the direct formation of a disubstituted iron μ-oxo dimer complex. The influence of meso-aryl substituents on the progress and products of the nitration reaction was investigated. In addition, to elucidate the most important factors which influence the redox reactivity of these different iron nitrosyl complexes, selected compounds were examined by cyclic voltammetry and thin-layer UV-visible or FTIR spectroelectrochemistry in CH(2)Cl(2).
authors.affiliation: Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata, via della Ricerca Scientifica, 1, 00133 Rome, Italy.
authors.forename: Sara
authors.initials: S
authors.lastname: Nardis
authors.forename: Manuela
authors.initials: M
authors.lastname: Stefanelli
authors.forename: Pruthviraj
authors.initials: P
authors.lastname: Mohite
authors.forename: Giuseppe
authors.initials: G
authors.lastname: Pomarico
authors.forename: Luca
authors.initials: L
authors.lastname: Tortora
authors.forename: Machima
authors.initials: M
authors.lastname: Manowong
authors.forename: Ping
authors.initials: P
authors.lastname: Chen
authors.forename: Karl M
authors.initials: KM
authors.lastname: Kadish
authors.forename: Frank R
authors.initials: FR
authors.lastname: Fronczek
authors.forename: Gregory T
authors.initials: GT
authors.lastname: McCandless
authors.forename: Kevin M
authors.initials: KM
authors.lastname: Smith
authors.forename: Roberto
authors.initials: R
authors.lastname: Paolesse
mesh_terms: D018360:Crystallography, X-Ray; D007501:Iron / Q000737:chemistry*; D008958:Models, Molecular; D009574:Nitro Compounds / Q000737:chemistry*; D011166:Porphyrins / Q000737:chemistry*; D016339:Spectrometry, Mass, Fast Atom Bombardment; D013056:Spectrophotometry, Ultraviolet
chemical_list: D009574:Nitro Compounds; D011166:Porphyrins; C431863:corrole; D007501:Iron