Nitration of iron corrolates: further evidence for non-innocence of the corrole ligand

Stefanelli, Manuela; Nardis, Sara; Tortora, Luca; Fronczek, Frank R.; Licoccia, Silvia; Paolesse, Roberto

doi:10.1039/c0cc05491g

Cited by 38 publications

(45 citation statements)

References 22 publications

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“…In this regard, we have recently shown that a nitration reaction carried out on an iron triarylcorrolate 12 confirmed the non-innocence 10,11 of the macrocyclic ligand in these complexes. With this, and previous results in mind, we decided to extend our initial study of the nitration reaction to other iron triarylcorrolates in order to investigate the scope of the synthetic method.…”

Section: Introductionmentioning

confidence: 73%

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β-Nitro Derivatives of Iron Corrolates

et al. 2012

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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 CH2Cl2.

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Section: Introductionmentioning

confidence: 73%

“…19 Spectroscopic data for 13 , 14 , 17 and 18 were in agreement with data reported earlier in the literature. 12 …”

Section: Methodsmentioning

confidence: 99%

β-Nitro Derivatives of Iron Corrolates

et al. 2012

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“…53,54 This type of reactivity has not yet been achieved with early transition metal corrole chemistry. However, the similar redox-active nature of corrole, as demonstrated by catalytic multi-electron chemistry with first row transition metal complexes, 4,55 suggests that reduction chemistry of some of the complexes presented here should be possible.…”

Section: Introductionmentioning

confidence: 73%

Recent developments in out-of-plane metallocorrole chemistry across the periodic table

Buckley

Arnold

2015

Dalton Trans.

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“…When copper or iron corroles were used as starting compounds, NaNO 2 could be used as the chemical reagent, because of the radical cation character of the copper and iron corroles (Eq. 3): 95,96 (Cor)Cu(III) (Cor)Cu(II) •+…”

Section: Substitution Of Nucleophiles Onto Corrolesmentioning

confidence: 99%

Electrosynthesis Processes Based on Oxidative Couplings of Porphyrins for the Formation of Supramolecular Assemblies

Schaming¹

2014

Handbook of Porphyrin Science (Volume 32)

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Nitration of iron corrolates: further evidence for non-innocence of the corrole ligand

Abstract: Mono- and di-substituted β-nitro derivatives have been obtained from the reaction of ttcorrFeCl with sodium nitrite in refluxing DMF. This result is unprecedented for iron corrolates and further evidences the non-innocent character of the corrole ligand.

Cited by 38 publications

References 22 publications

β-Nitro Derivatives of Iron Corrolates

β-Nitro Derivatives of Iron Corrolates

Recent developments in out-of-plane metallocorrole chemistry across the periodic table

Electrosynthesis Processes Based on Oxidative Couplings of Porphyrins for the Formation of Supramolecular Assemblies

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