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

Elsa Follet, Peter Mayer, Guillaume Berionni

Résultats de recherche: Recherche - Revue par des pairsArticle

Résumé

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.

langueAnglais
Pages623-630
Nombre de pages8
journalChemistry - A European Journal
Volume23
Numéro3
Les DOIs
étatPublié - 12 janv. 2017
Modification externeOui

Empreinte digitale

Acidity
Ions
Lewis Bases
Pyridines
Lewis Acids
Nucleophiles
Equilibrium constants
Alkalinity
Phosphorus
Catalysis
Nitrogen
Carbon
Tuning
X rays
Kinetics

mots-clés

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    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.",
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    Structures, Lewis Acidities, Electrophilicities, and Protecting Group Abilities of Phenylfluorenylium and Tritylium Ions. / Follet, Elsa; Mayer, Peter; Berionni, Guillaume.

    Dans: Chemistry - A European Journal, Vol 23, Numéro 3, 12.01.2017, p. 623-630.

    Résultats de recherche: Recherche - Revue par des pairsArticle

    TY - JOUR

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    AU - Mayer,Peter

    AU - Berionni,Guillaume

    PY - 2017/1/12

    Y1 - 2017/1/12

    N2 - 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.

    AB - 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.

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    KW - electrophilicity scales

    KW - Lewis acid catalysts

    KW - Lewis acidity scales

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