Corroles demetallation

Coproporphyrin I synthesis, 816 Coronands classification, 919 metal ion complexes, 928,938 Corphins, 855 Coninoids, 983 Corrins, 871-888 demetallation, 882 deuteration, 879 electrophilic reactions, 879 metallation, 882 NMR, 878 nucleophilicity, 886 nucleophilic reactions, 879 oxidation, 879 oxidative lactamization, 880 oxidative lactonization, 880 photochemistry, 887 reactions, 879 at metal, 885 rearrangements, 879 redox chemistry, 888 spectra, 877 synthesis, 878 Corroles, 871-888 demetallation, 874 deuteration, 872 hydrogenation, 872 metallation, 874 reactions, 872 at metal, 875 redox chemistry, 876 synthesis, 871 Corticotropin zinc complexes medical use, 966 Cotton effect anils, 717... 

In another approach, bis(dipyrrin) 23 (Scheme 12) with Mn(II) acetate and molecular oxygen furnished corrole Mn(III) complex 24 (01JCS(CC)2336). Complex 24 with HBr in AcOH furnished the corresponding demetallated corrole. 

In spite of the above, and in spite of what might have been inferred from the early papers, the Cu and Co oxacorroles 2.17 and 2.18 were apparently successfully made by the Johnson group. These, in turn, were later demetalated successfully using sulfuric acid to give the metal-free species 2.19. This metal-free corrole was reported to react further with various metal salts to afford the corresponding meta-lated derivatives. Unfortunately, however, specific details as to which metals were used and the properties of the resulting metallocorroles were never presented in the open literature. They are thus not known to the present authors. 

Significant work has been performed on the corrole complexes of four second-row transition metals Mo, Ru, Rh, and Ag. The spectroscopic properties of a number of (oxo)Mo(V) corroles have been examined in detail. Meanwhile, a number of dimeric Ru corroles have been synthesized and their electrochemical properties have been reported monomeric Ru-NO corroles have also been disclosed. The syntheses of both Rh(I) and Rh(III) corroles have been reported by a number of groups, and the excited-state EPR spectroscopy of the Rh(III) derivatives has been presented. High-valent Ag(III) corroles have been studied extensively with regards to their facile demetalation. 

Stefanelli M, Shen J, Zhu W, Mastroianni M, Mandoj F, Nardis S, Ou Z, Kadish KM, Fronczek FR, Smith KM, Paolesse R (2009) Demetalation of silver(III) corrolates. Inorg Chem 48 6879-6887... 

Capar C, Thomas KE, Ghosh A (2008) Reductive demetalation of copper corroles first simple route to free-base P-octabromocorroles. J Porphyr Phthalocyanines 12 964-967... 

Capar C, Hansen LK, Conradie J, Ghosh A (2010) P-octabromo-me.s0-tris(pentafluoro-phenyl)corrole reductive demetalation-based synthesis of a heretofore inaccessible, perhalo-genated free-base corrole. J Porphyr Phthalocyanines 14 509-512... 

MetaUtttion and demetallation Usually corroles are metallated with metal salts or metal carbonyls (Scheme... 

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