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. 2012 Mar 19;51(6):3910-20.
doi: 10.1021/ic3002459. Epub 2012 Mar 6.

β-Nitro derivatives of iron corrolates

Sara Nardis  1 , Manuela Stefanelli, Pruthviraj Mohite, Giuseppe Pomarico, Luca Tortora, Machima Manowong, Ping Chen, Karl M Kadish, Frank R Fronczek, Gregory T McCandless, Kevin M Smith, Roberto Paolesse
Affiliations

β-Nitro derivatives of iron corrolates

Sara Nardis et al. Inorg Chem. .

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).

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Figures

Figure 1
Figure 1
The two independent Fe corroles 17, a) Fe1 complex and b) Fe2 complex, in the unit cell are shown in approximately the same orientation to illustrate how the respective substituents differ in orientation.
Figure 2
Figure 2
The packing relationship between Fe1 corrole and Fe2i corrole related by the symmetry code: (i) −x+1, −y, −z+1. The orientation of the axial nitrosyl ligand in each complex is pointed towards each other with a short intermolecular O1···O6i distance of 2.897 (3) Å.
Figure 3
Figure 3
Cyclic voltammograms of (TMOPC)FeNO 9, 3-NO2-(TMOPC)FeNO 15 and 3,17-(NO2)2-(TMOPC)FeNO 19 in CH2Cl2 containing 0.1 M TBAP. The reduction peaks of 19 marked by asterisks are mostly likely due to Fe species with an unknown sixth axial ligand.
Figure 4
Figure 4
Cyclic voltammograms of (TNPC)FeNO 10 and 3,17-(NO2)2-(TNPC)FeNO 20 in CH2Cl2 containing 0.1 M TBAP.
Figure 5
Figure 5
Correlation between the number of nitro groups on the corrole macrocycle and E1/2 for the first reduction and the first oxidation in CH2Cl2, 0.1 M TBAP of (a) (NO2)xTNPCFeIIINO (10, 16 and 20) and (NO2)xTMOPCFeIIINO (9, 15 and 19), (b) (NO2)xTtBuPCorrCuIII and (c) (NO2)xTPCorrGeIV(OCH3). Data for the Cu(III) and Ge(IV) compounds were taken form Refs. and .
Figure 6
Figure 6
Thin-layer UV-vis spectral changes of 15 during the first and the second oxidation in CH2Cl2, 0.2 M TBAP.
Figure 7
Figure 7
UV-visible changes recorded during the first reduction of (a) (NO2)x(TMOPC)FeNO (Goup A) and (b) (NO2)x(TNPC)FeNO (Group B) in CH2Cl2, 0.1 M TBAP.
Figure 8
Figure 8
Thin-layer IR spectral changes during the first one-electron reduction of (a) 15 and (b) 19 in CH2Cl2, 0.1 M TBAP upon the indicated potentials.
Scheme 1
Scheme 1
Nitration of triarylcorroles.
Chart 1
Chart 1
Structures of the electrochemically investigated compounds.
See this image and copyright information in PMC

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