One Carbon Ring Expansion of Bipyrrole to Bipyridine Enables Access to a π-Extended, Non-innocent, Corrole-like Ligand

Abstract

A π-extended, diaza-triphenylene embedded, mono-anionic corrole analogue and its Ni^II complex were synthesized from a diaza-triphenylene precursor, which was obtained from a double one-carbon insertion into a naphthobipyrrole diester. Following conversion to the corresponding activated diol and acid-catalyzed condensation with pyrrole, subsequent reaction with pentafluorobenzaldehyde afforded mono-anionic, π-extended bipyricorrole-like macrocycle. Attempted Ni^II insertion with Ni(OAc)₂ ⋅ 4H₂ O resulted an ESR active, Ni^II bipyricorrole radical complex, which was converted to a stable cationic Ni^II complex upon treatment with [(Et₃ O)⁺ (SbCl₆ )^- ]. Both complexes were characterized by ¹ H and ¹³ C NMR, UV/Vis spectroscopy and single crystal X-ray diffraction analysis. The Ni^II bipyricorrole radical complex is converted to a cationic Ni^II complex by single-electron reduction using cobaltocene. Both the cationic Ni^II complex and the radical Ni^II complex exhibited ligand-centered redox behavior, whereas the Ni^II remains in the +2 oxidation state.

Keywords: carbene insertion; corroles; diazatriphenylenes; nickel; radical complexes.