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

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 subvert...

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Main Authors: Ross A. Jackson, Nicholas J. Evans, Dawid J. Babula, Thomas M. Horsley Downie, Rex S. C. Charman, Samuel E. Neale, Mary F. Mahon, David J. Liptrot
Format: Article
Language:English
Published: Nature Portfolio 2025-01-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-56544-z
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author Ross A. Jackson
Nicholas J. Evans
Dawid J. Babula
Thomas M. Horsley Downie
Rex S. C. Charman
Samuel E. Neale
Mary F. Mahon
David J. Liptrot
author_facet Ross A. Jackson
Nicholas J. Evans
Dawid J. Babula
Thomas M. Horsley Downie
Rex S. C. Charman
Samuel E. Neale
Mary F. Mahon
David J. Liptrot
author_sort Ross A. Jackson
collection DOAJ
description 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.
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spelling doaj-art-334604d2aad94f46a4b7e7bbee17cbbc2025-02-02T12:31:28ZengNature PortfolioNature Communications2041-17232025-01-011611810.1038/s41467-025-56544-zNucleophilicity at copper(-I) in a compound with a Cu–Mg bondRoss A. Jackson0Nicholas J. Evans1Dawid J. Babula2Thomas M. Horsley Downie3Rex S. C. Charman4Samuel E. Neale5Mary F. Mahon6David J. Liptrot7Department of Chemistry, University of BathDepartment of Chemistry, University of BathDepartment of Chemistry, University of BathDepartment of Chemistry, University of BathDepartment of Chemistry, University of BathDepartment of Chemistry, University of BathDepartment of Chemistry, University of BathDepartment of Chemistry, University of BathAbstract 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.https://doi.org/10.1038/s41467-025-56544-z
spellingShingle Ross A. Jackson
Nicholas J. Evans
Dawid J. Babula
Thomas M. Horsley Downie
Rex S. C. Charman
Samuel E. Neale
Mary F. Mahon
David J. Liptrot
Nucleophilicity at copper(-I) in a compound with a Cu–Mg bond
Nature Communications
title Nucleophilicity at copper(-I) in a compound with a Cu–Mg bond
title_full Nucleophilicity at copper(-I) in a compound with a Cu–Mg bond
title_fullStr Nucleophilicity at copper(-I) in a compound with a Cu–Mg bond
title_full_unstemmed Nucleophilicity at copper(-I) in a compound with a Cu–Mg bond
title_short Nucleophilicity at copper(-I) in a compound with a Cu–Mg bond
title_sort nucleophilicity at copper i in a compound with a cu mg bond
url https://doi.org/10.1038/s41467-025-56544-z
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