Gesellschaft Deutscher Chemiker
Keine Benachrichtigungen
Sie haben noch keine Lesezeichen
Abmelden

Artikel

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

Von Wiley-VCH zur Verfügung gestellt

Diazatriphenylene was synthesized by a double, one-carbon-insertion reaction. Following elaboration, this key precursor allowed access to an unprecedented NiII-bipyricorrole radical and a cationic square planar complex upon one-electron oxidation.


Abstract

A π-extended, diaza-triphenylene embedded, mono-anionic corrole analogue and its NiII 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 NiII insertion with Ni(OAc)2 ⋅ 4H2O resulted an ESR active, NiII bipyricorrole radical complex, which was converted to a stable cationic NiII 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 NiII bipyricorrole radical complex is converted to a cationic NiII complex by single-electron reduction using cobaltocene. Both the cationic NiII complex and the radical NiII complex exhibited ligand-centered redox behavior, whereas the NiII remains in the +2 oxidation state.

Zum Volltext

Überprüfung Ihres Anmeldestatus ...

Wenn Sie ein registrierter Benutzer sind, zeigen wir in Kürze den vollständigen Artikel.