Reactivity-Tuning in Frustrated Lewis Pairs: Nucleophilicity and Lewis Basicity of Sterically Hindered Phosphines

Elsa Follet, Peter Mayer, David S. Stephenson, Armin R. Ofial, Guillaume Berionni

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

The nucleophilicity and Lewis basicity of sterically hindered phosphines, widely used in catalysis and in frustrated Lewis pair (FLP) chemistry, have been quantified by determining the rates and equilibrium constants of their associations with reference systems (benzhydrylium and tritylium ions) of calibrated electrophilicities and Lewis acidities. These structure–reactivity investigations allow a rationalization of the Lewis acid–base interactions all along the way from covalent Lewis adducts to FLPs. Comparisons of the association of phosphines of increasing sizes (Ph3P, (o-tolyl)3P, and tBu3P) with the triarylborane B(C6F5)3 and with the isoelectronic tritylium ions Ar3C+ provide detailed insights for the future fine-tuning of the reactivities of FLPs. As a proof of concept, tritylium-ion-derived FLPs were shown to react with alkynes, as reported for the FLPs derived from the benchmark triarylborane B(C6F5)3.

langueAnglais
Pages7422-7427
Nombre de pages6
journalChemistry - A European Journal
Volume23
Numéro31
Les DOIs
étatPublié - 2017
Modification externeOui

Empreinte digitale

Phosphines
Alkalinity
Tuning
Ions
Lewis Acids
Alkynes
Equilibrium constants
Acidity
Catalysis
Rate constants
Association reactions
Acids

mots-clés

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    Follet, Elsa ; Mayer, Peter ; Stephenson, David S. ; Ofial, Armin R. ; Berionni, Guillaume. / Reactivity-Tuning in Frustrated Lewis Pairs : Nucleophilicity and Lewis Basicity of Sterically Hindered Phosphines. Dans: Chemistry - A European Journal. 2017 ; Vol 23, Numéro 31. p. 7422-7427.
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    abstract = "The nucleophilicity and Lewis basicity of sterically hindered phosphines, widely used in catalysis and in frustrated Lewis pair (FLP) chemistry, have been quantified by determining the rates and equilibrium constants of their associations with reference systems (benzhydrylium and tritylium ions) of calibrated electrophilicities and Lewis acidities. These structure–reactivity investigations allow a rationalization of the Lewis acid–base interactions all along the way from covalent Lewis adducts to FLPs. Comparisons of the association of phosphines of increasing sizes (Ph3P, (o-tolyl)3P, and tBu3P) with the triarylborane B(C6F5)3 and with the isoelectronic tritylium ions Ar3C+ provide detailed insights for the future fine-tuning of the reactivities of FLPs. As a proof of concept, tritylium-ion-derived FLPs were shown to react with alkynes, as reported for the FLPs derived from the benchmark triarylborane B(C6F5)3.",
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    Reactivity-Tuning in Frustrated Lewis Pairs : Nucleophilicity and Lewis Basicity of Sterically Hindered Phosphines. / Follet, Elsa; Mayer, Peter; Stephenson, David S.; Ofial, Armin R.; Berionni, Guillaume.

    Dans: Chemistry - A European Journal, Vol 23, Numéro 31, 2017, p. 7422-7427.

    Résultats de recherche: Contribution à un journal/une revueArticle

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