Enhancing the Nucleophilicity of Aluminyl Anions:  Targeting Selective C–H Activation

Fabian Kallmeier; Gareth R. Nelmes; Claire L. McMullin; Alison J. Edwards; Jamie Hicks

doi:10.1039/d5sc02682b

Enhancing the Nucleophilicity of Aluminyl Anions: Targeting Selective C–H Activation

Fabian Kallmeier, Gareth R. Nelmes, Claire L. McMullin, Alison J. Edwards, Jamie Hicks

Department of Chemistry

The Australian National University

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

Abstract

Anionic aluminium(I) complexes, or aluminyl anions, are a recently discovered class of main group compounds that can C–H activate simple aromatic molecules. However, functional group tolerance remains an issue, with the activation of functionalised arenes often favouring more kinetically accessible side reactions (e.g. C–O/C–F activation) over the desired C–H activation. Here, we report a new, electron-rich potassium aluminyl complex, which by DFT has been calculated to be the most nucleophilic diamido aluminyl anion reported to date. The anion shows unprecedented rates of reaction towards the C–H activation of arenes, achieving the C–H activation of stoichiometric benzene in seconds at room temperature. Furthermore, the C–H activation is selective even in a range of functionalised arenes, including those with C–O and C–F bonds.

Original language	English
Journal	Chemical Science
Early online date	13 May 2025
DOIs	https://doi.org/10.1039/d5sc02682b
Publication status	E-pub ahead of print - 13 May 2025

Data Availability Statement

The data supporting this article have been included as part of the Supplementary Information. Finalised CIFs for all X-ray diffraction structures have been deposited at the Cambridge Crystallographic Data Centre. These can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif or by emailing [email protected].

Acknowledgements

The authors would like to acknowledge the award of neutron beam-time on the KOALA2 instrument at ANSTO (Proposal 18886). This research was undertaken with the assistance of resources from the National Computational Infrastructure (NCI Australia), an NCRIS enabled capability supported by the Australian Government, and the University of Bath’s Research Computing (doi.org/10.15125/b6cd-s854) for their support in this work.

Funding

JH would like to thank the Australian Research Council (FT240100229) for the funding of this work. We acknowledge the support of the Australian Centre for Neutron Scattering, ANSTO and the Australian Government through the National Collaborative Research Infrastructure Strategy supporting the neutron research infrastructure in this work via ACNS proposal 18886. This research was undertaken with the assistance of resources from the National Computational Infrastructure (NCI Australia), an NCRIS enabled capability supported by the Australian Government, and the University of Bath's Research Computing Group ( https://doi.org/10.15125/b6cd-s854 ) for their support in this work.

Funders	Funder number
National Computational Infrastructure
University of Bath
Australian Research Council	FT240100229
Government of Western Australia	18886

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Cite this

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abstract = "Anionic aluminium(I) complexes, or aluminyl anions, are a recently discovered class of main group compounds that can C–H activate simple aromatic molecules. However, functional group tolerance remains an issue, with the activation of functionalised arenes often favouring more kinetically accessible side reactions (e.g. C–O/C–F activation) over the desired C–H activation. Here, we report a new, electron-rich potassium aluminyl complex, which by DFT has been calculated to be the most nucleophilic diamido aluminyl anion reported to date. The anion shows unprecedented rates of reaction towards the C–H activation of arenes, achieving the C–H activation of stoichiometric benzene in seconds at room temperature. Furthermore, the C–H activation is selective even in a range of functionalised arenes, including those with C–O and C–F bonds.",

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AU - Kallmeier, Fabian

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AU - Edwards, Alison J.

AU - Hicks, Jamie

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AB - Anionic aluminium(I) complexes, or aluminyl anions, are a recently discovered class of main group compounds that can C–H activate simple aromatic molecules. However, functional group tolerance remains an issue, with the activation of functionalised arenes often favouring more kinetically accessible side reactions (e.g. C–O/C–F activation) over the desired C–H activation. Here, we report a new, electron-rich potassium aluminyl complex, which by DFT has been calculated to be the most nucleophilic diamido aluminyl anion reported to date. The anion shows unprecedented rates of reaction towards the C–H activation of arenes, achieving the C–H activation of stoichiometric benzene in seconds at room temperature. Furthermore, the C–H activation is selective even in a range of functionalised arenes, including those with C–O and C–F bonds.

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Enhancing the Nucleophilicity of Aluminyl Anions: Targeting Selective C–H Activation

Abstract

Data Availability Statement

Acknowledgements

Funding

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Enhancing the Nucleophilicity of Aluminyl Anions: Targeting Selective C–H Activation

Abstract

Data Availability Statement

Acknowledgements

Funding

Access to Document

Other files and links

Fingerprint

Equipment

Anatra HTC cluster

Cite this