| Abstract: | Different pathways for the preparation of organometallic manganese(IV) corroles with σ‐aryl ligands have been evaluated. The treatment of a manganese(III) corrole with Grignard reagents PhMgX (X = Cl, Br), followed by aerial oxidation yields oxidized halogenido complexes (cor)MnIVX] instead of the anticipated organometallic compounds. Reaction of these halogenido species, especially the bromido compound, with excess Grignard reagents or with lithium aryls results in the formation of the desired σ‐aryl compounds via salt metatheses. Three examples of this class of rare complexes have been characterized by means of optical and 1H NMR spectroscopy, and in two cases single crystal X‐ray diffraction studies have been carried out. In the crystal, the molecular structures of the σ‐phenyl‐ and the σ‐(p‐bromophenyl) derivatives were observed to be very similar, albeit both species pack in different pattern. |
