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

Autor: Srinivas Samala, Ji Hye Lee, Yeonju Park, Seong‐Jin Hong, Hongil Jo, Hyonseok Hwang, Young Mee Jung, Kang Min OK, Jonathan L. Sessler, Chang‐Hee Lee
Rok vydání: 2023
Předmět:
Zdroj: Chemistry – A European Journal. 29
ISSN: 1521-3765
0947-6539
Popis: 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 and subsequent reaction with pentafluorobenzaldehyde, afforded mono-anionic, π-extended bipyricorrole-like macrocycle. Attempted Ni(II) insertion with Ni(OAc)2•4H2O resulted an ESR active, Ni(II) bipyricorrole radical complex, which is converted to stable cationic Ni(II) complex upon treatment with [(Et3O)+(SbCl6)-]. Both complexes were characterized by 1H- and 13C-NMR, UV-vis spectroscopy and single crystal X-ray diffraction analysis. The Ni(II) bipyricorrole radical complex is converted to cationic Ni(II) complex by single electron reduction using cobaltocene. Both cationic Ni(II) complex and radical Ni(II) complex exhibit ligand-centered redox behavior while the Ni(II) remains in the +2 oxidation state.
Databáze: OpenAIRE
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