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

Research output: Contribution to journalArticle

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.

Original languageEnglish
Pages (from-to)7422-7427
Number of pages6
JournalChemistry - A European Journal
Volume23
Issue number31
DOIs
Publication statusPublished - 2017
Externally publishedYes

Keywords

  • frustrated Lewis pairs
  • Lewis adducts
  • Lewis bases
  • phosphines
  • reactivity scales

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  • Datasets

    CCDC 1521274: Experimental Crystal Structure Determination

    Berionni, G. (Contributor), Follet, E. (Contributor), Mayer, P. (Contributor), Ofial, A. R. (Contributor) & Stephenson, D. S. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017

    Dataset

    CCDC 1521275: Experimental Crystal Structure Determination

    Berionni, G. (Contributor), Follet, E. (Contributor), Mayer, P. (Contributor), Ofial, A. R. (Contributor) & Stephenson, D. S. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017

    Dataset

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