Nucleophilicity at copper(-I) in a compound with a Cu-Mg bond.

Jackson, Ross A; Evans, Nicholas J; Babula, Dawid J; Horsley Downie, Thomas M; Charman, Rex S C; Neale, Samuel E; Mahon, Mary F; Liptrot, David J · Nat Commun · 2025

basic_science · Level V

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Abstract

Copper is ubiquitous as a structural material, and as a reagent in (bio)chemical transformations. A vast number of chemical reactions rely on the near-inevitable preference of copper for positive oxidation states to make useful compounds. Here we show this electronic paradigm can be subverted in a stable compound with a copper-magnesium bond, which conforms to the formal oxidation state of Cu(-I). The Cu-Mg bond is synthesized by the reaction of an N-heterocyclic carbene (NHC) ligated copper alkoxide with a dimeric magnesium(I) compound. Its identity is confirmed by single-crystal X-ray structural analysis and NMR spectroscopy, and computational investigations provide data consistent with a high charge density at copper. The Cu-Mg bond acts as a source of the cupride anion, transferring the NHC-copper fragment to electrophilic s-, p-, and d-block atoms to make known and new copper-containing compounds.