Iron corrole

Similarly, the corresponding nickel complex, based on ESR spectroscopy, should be formulated as a nickel(II) corrole-71-radical. The iron corroles exist in the oxidation state + 111 or + IV depending on the nature of additional axial ligands. 

A more practical, atom-economic and environmentally benign aziridination protocol is the use of chloramine-T or bromamine-T as nitrene source, which leads to NaCl or NaBr as the sole reaction by-product. In 2001, Gross reported an iron corrole catalyzed aziridination of styrenes with chloramine-T [83]. With iron corrole as catalyst, the aziridination can be performed rmder air atmosphere conditions, affording aziridines in moderate product yields (48-60%). In 2004, Zhang described an aziridination with bromamine-T as nitrene source and [Fe(TTP)Cl] as catalyst [84]. This catalytic system is effective for a variety of alkenes, including aromatic, aliphatic, cyclic, and acyclic alkenes, as well as cx,p-unsaturated esters (Scheme 28). Moderate to low stereoselectivities for 1,2-disubstituted alkenes were observed indicating the involvement of radical intermediate. 

Table 8. Electronic spectra of iron corrolates. According to Refs. [27, 28].

Fe3+ derivatives of porphyrins and chlorins are all high spin in the absence of N-donor axial ligands and in chlorinated solvents [41,42] the low spin state observed in the case of iron corrolate demonstrates that the ligand field strength of corrole is very different from that of other macrocycles. 

Matsuo T, Hayashi A, Abe M et al (2009) Meso-unsubstituted iron corrole in hemoproteins remarkable differences in effects on peroxidase activities between myoglobin and horseradish peroxidase. J Am Chem Soc 131 15124-15125... 

Stefanelli M, Nardis S, Tortora L, Fronczek FR, Smith KM, Licoccia S, Paolesse R (2011) Nitration of iron corrolates further evidence for non-innocence of the corrole ligand. Chem Commun 47 4255 1257... 

Cai S, Walker FA, Licoccia S (2000) NMR and EPR investigations of iron corrolates iron (III) corrolate 7t cation radicals or iron(IV) corrolates Inorg Chem 39 3466-3478... 

Simkhovich L, Gross Z (2004) Halogeno-coordinated iron corroles. Inorg Chem 43 ... 

Walker FA, Licoccia S, Paolesse R (2006) Iron corrolates unambiguous chloroiron(III) (corrolate)2" 7t-cation radicals. J Inorg Biochem 100 810-837... 

Ye S, Tuttle T, Bill E, Simkhovich L, Gross Z, Thiel W, Neese F (2008) The electronic structure of iron corroles a combined experimental and quantum chemical study. Chem Eur J 14 10839-10851... 

Grodkowski J, Neta P, Fujita E, Mahammed A, Simkhovich L, Gross Z (2002) Reduction of cobalt and iron corroles and catalyzed reduction of C02. J Phys Chem A 106 4772 -778... 

Schwalbe M, Dogutan DK, Stoian SA, Teets TS, Nocera DG (2011) Xanthene-modified and hangman iron corroles. Inorg Chem 50 1368-1377... 

Structure 5.16. Corrole structures of different metals. Reprinted from Figure in the Experimental Section J. Grodkowski, R Neta, E. Fujita, A. Mahammed, L. Simkhovich and Z. Gross, Reduction of cobalt and iron corroles and catalyzed reduction of CO2, Journal of Physical Chemistry A 106(18), 4772 778 (2002). Copyright 2002, with permission of American Chemical Society. 

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