The isolation and characterization of formally high-valent copper(III) complexes is critical to permit a rigorous examination of the molecular structure and assess the underlying electronic configuration. Here, we present a cuprous dinitrogen complex situated within a hydridancene-flanked dipyrrin ligand platform. Facile displacement of dinitrogen is observed with a variety of weakly coordinating ligands, representing a zero-dimensional porous molecular species. Treatment with aryl azides affords a terminal copper nitrene complex with the oxidation residing exclusively on the nitrenoid fragment as ascertained by quantum calculations and multinuclear x-ray absorption spectroscopy. Electrophilic nitrene transfer into unactivated C–H bonds is observed, supporting the intermittency of a copper nitrenoid motif in copper-faciliated C–H amination. Air exposure of the cuprous dinitrogen complex affords a side-bound cupric superoxide species in which the dioxygen coordination is readily manipulated through redox processes and ligand exchange. These findings are contextualized in a broader reassignment of high-valent copper(III) complexes in which ligand field inversion is general.<br/>

Ligand field inversion in sterically encumbered copper dipyrrin complexes

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.