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

Ross Jackson; Nick Evans; Dawid Babula; Thomas Horsley Downie; Rex Charman; Sam Neale; Mary Mahon; David Liptrot

doi:10.1038/s41467-025-56544-z

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

Ross Jackson, Nick Evans, Dawid Babula, Thomas Horsley Downie, Rex Charman, Sam Neale, Mary Mahon, David Liptrot

Research output: Contribution to journal › Article › peer-review

2 Citations (SciVal)

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.

Original language	English
Article number	1101
Pages (from-to)	1101
Number of pages	1
Journal	Nature Communications
Volume	16
Issue number	1
DOIs	https://doi.org/10.1038/s41467-025-56544-z
Publication status	Published - Dec 2025

Bibliographical note

Publisher Copyright:
© The Author(s) 2025.

Data Availability Statement

Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2363357 (1), 2363358 (2), 2363359 (3), 2363360 (4), 2265494 (5), 2363361 (6), 2363362 (7), and 2408960 ([(6-Dipp)CuOEt]). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. Source Data are provided with this manuscript. All other experimental, computational, crystallographic, and spectroscopic data are available in the Supplementary Information. All data are available from the corresponding author upon request. Source data are provided with this paper.

Acknowledgements

DJL thanks the Royal Society for a University Research Fellowship. This research made use of the Anatra High Performance Computing (HPC) Services at the University of Bath. (University of Bath, Research Computing Group, https://doi.org/10.15125/b6cd-s854 ). We also thank Dr Claire McMullin for use of the AIMAll and NBO software for electronic structure calculations. Funding: Royal Society University Research Fellowship URF\R1\191066 (DJL), EPSRC Standard Research Grant EP/X01181X/1 (SEN).

Funding

DJL thanks the Royal Society for a University Research Fellowship. This research made use of the Anatra High Performance Computing (HPC) Services at the University of Bath. (University of Bath, Research Computing Group, https://doi.org/10.15125/b6cd-s854). We also thank Dr Claire McMullin for use of the AIMAll and NBO software for electronic structure calculations. Funding: Royal Society University Research Fellowship URF\\R1\\191066 (DJL), EPSRC Standard Research Grant EP/X01181X/1 (SEN).

Funders	Funder number
Royal Society
University of Bath	URF\R1\191066
Engineering and Physical Sciences Research Council	EP/X01181X/1

ASJC Scopus subject areas

General Chemistry
General Biochemistry,Genetics and Molecular Biology
General Physics and Astronomy

Access to Document

10.1038/s41467-025-56544-zLicence: CC BY

Cite this

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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.",

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AU - Neale, Sam

AU - Mahon, Mary

AU - Liptrot, David

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

Abstract

Bibliographical note

Data Availability Statement

Acknowledgements

Funding

ASJC Scopus subject areas

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Molecular s-block Assemblies for Redox-active Bond Activation and Catalysis: Repurposing the s-block as 3d-elements

Cite this

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

Abstract

Bibliographical note

Data Availability Statement

Acknowledgements

Funding

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Projects

Molecular s-block Assemblies for Redox-active Bond Activation and Catalysis: Repurposing the s-block as 3d-elements

Cite this