One-Pot Synthesis of a bis-Pocket Corrole through a 14-fold Bromination Reaction.

A one-pot protocol, effecting 14-fold bromination with elemental bromine, has afforded copper β-octabromo--tris(2,6-dibromo-3,5-dimethoxyphenyl)corrole, a new bis-pocket metallocorrole. The Cu complex underwent smooth demetalation under reductive conditions, affording the free corrole ligand, which in turn could be readily complexed to Mn and Au. A single-crystal X-ray structure was obtained for the Mn complex.

Ligand noninnocence in FeNO corroles: insights from β-octabromocorrole complexes.

The first FeNO octabromocorroles have been synthesized including four β-octabromo-meso-tris(p-X-phenyl)corrole derivatives Fe[Br8TpXPC](NO) (X = CF3, H, CH3, OCH3) and the β-octabromo-meso-tris(pentafluorophenyl)corrole complex, Fe[Br8TPFPC](NO). The last complex, which proved amenable to single-crystal X-ray structure determination, exhibits the geometry parameters: Fe-N(O) 1.643(8) Å, N-O 1.

Cryptic noninnocence: FeNO corroles in a new light.

Multiple lines of evidence, including electronic absorption spectroscopy, infrared spectroscopy, and broken-symmetry DFT calculations, indicate that the well-known FeNO corroles, long assumed to be {FeNO}(6) complexes, are in fact better described as {FeNO}(7)-(corrole˙(2-)).