Dynamic activation of alcohols by an electrophilic phosphinine

Richard O. Kopp; Massimo Rigo; Lucie J. Groth; Nathan T. Coles; Samuel E. Neale; Samantha Frank; Moritz J. Ernst; Manuela Weber; Christian Müller

doi:10.1039/d5cc05302a

Dynamic activation of alcohols by an electrophilic phosphinine

Richard O. Kopp, Massimo Rigo, Lucie J. Groth, Nathan T. Coles, Samuel E. Neale, Samantha Frank, Moritz J. Ernst, Manuela Weber, Christian Müller

Department of Chemistry

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

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.

Original language	English
Pages (from-to)	18625-18628
Number of pages	4
Journal	Chemical communications (Cambridge, England)
Volume	61
Issue number	94
Early online date	17 Oct 2025
DOIs	https://doi.org/10.1039/d5cc05302a
Publication status	Published - 20 Nov 2025

Data Availability Statement

The data supporting this article have been included as part of the Supplementary information (SI). Supplementary information is available. See DOI: https://doi.org/10.1039/d5cc05302a.

CCDC 2487210 (2) and 2487209 (3) contain the supplementary crystallographic data for this paper.18a,b

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Catalysis
Ceramics and Composites
General Chemistry
Surfaces, Coatings and Films
Metals and Alloys
Materials Chemistry

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AU - Kopp, Richard O.

AU - Rigo, Massimo

AU - Groth, Lucie J.

AU - Coles, Nathan T.

AU - Neale, Samuel E.

AU - Frank, Samantha

AU - Ernst, Moritz J.

AU - Weber, Manuela

AU - Müller, Christian

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N2 - 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.

AB - 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.

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ER -

Dynamic activation of alcohols by an electrophilic phosphinine

Abstract

Data Availability Statement

ASJC Scopus subject areas

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