Structures, Lewis Acidities, Electrophilicities, and Protecting Group Abilities of Phenylfluorenylium and Tritylium Ions

Elsa Follet, Peter Mayer, Guillaume Berionni

Research output: Contribution to journalArticle

Abstract

The isolation, characterization, and the first X-ray structures of a fluorenylium ion and its Lewis adducts with nitrogen- and phosphorus-centered Lewis bases are reported. Kinetics of the reactions of a series of fluorenylium ions with reference π-, σ-, and n-nucleophiles of various sizes and nucleophilicities allowed the interplay between electronic and structural parameters on the electrophilicities of these planarized tertiary carbenium ions to be elucidated. Structure–reactivity correlations and extensive comparisons of their reactivities with those of di- and triarylcarbenium ions are described. Quantitative determination of the electrofugalities of fluorenylium ions revealed to which extent they are complementing tritylium ions as protecting groups and how their tuning is possible. Determination of the equilibrium constants of the Lewis adducts formation between pyridines of calibrated Lewis basicities and phenylfluorenylium and tritylium ions allowed the determination of their Lewis acidities and to showcase the potential of these carbon-centered Lewis acids in catalysis.

Original languageEnglish
Pages (from-to)623-630
Number of pages8
JournalChemistry - A European Journal
Volume23
Issue number3
DOIs
Publication statusPublished - 12 Jan 2017
Externally publishedYes

Keywords

  • carbocations
  • electrophilicity scales
  • Lewis acid catalysts
  • Lewis acidity scales
  • protecting groups

Fingerprint Dive into the research topics of 'Structures, Lewis Acidities, Electrophilicities, and Protecting Group Abilities of Phenylfluorenylium and Tritylium Ions'. Together they form a unique fingerprint.

  • Datasets

    CCDC 1495228: Experimental Crystal Structure Determination

    Berionni, G. (Contributor), Follet, E. (Contributor) & Mayer, P. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017

    Dataset

    CCDC 1495226: Experimental Crystal Structure Determination

    Berionni, G. (Contributor), Follet, E. (Contributor) & Mayer, P. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017

    Dataset

    CCDC 1495227: Experimental Crystal Structure Determination

    Berionni, G. (Contributor), Follet, E. (Contributor) & Mayer, P. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017

    Dataset

    Cite this