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Dynamic activation of alcohols by an electrophilic phosphinine

Kopp, Richard O., Rigo, Massimo, Groth, Lucie J., Coles, Nathan T. ORCID: https://orcid.org/0000-0001-6190-9080, Neale, Samuel E., Frank, Samantha, Ernst, Moritz J., Weber, Manuela and Müller, Christian 2025. Dynamic activation of alcohols by an electrophilic phosphinine. Chemical Communications 10.1039/d5cc05302a

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Abstract

A bis(trifluoromethyl)-substituted phosphinine undergoes reversible oxidative addition of primary and secondary alcohols at the low-coordinate phosphorus(iii) atom. This unprecedented reactivity contrasts the general inertness of uncoordinated phosphinines toward protic substrates and provides a rare example of reversible alcohol activation mediated by a main-group element compound. DFT calculations suggest that a hydrogen-bonded methanol network enables the transformation, offering a new concept for dynamic E–H bond activation by electrophilic, aromatic phosphorus heterocycles.

Item Type: Article
Date Type: Published Online
Status: In Press
Schools: Schools > Chemistry
Additional Information: License information from Publisher: LICENSE 1: URL: https://creativecommons.org/licenses/by/3.0/, Start Date: 2025-10-17
Publisher: Royal Society of Chemistry
ISSN: 1359-7345
Date of First Compliant Deposit: 5 November 2025
Date of Acceptance: 15 October 2025
Last Modified: 06 Nov 2025 02:30
URI: https://orca.cardiff.ac.uk/id/eprint/182131

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