9-Phosphatriptycene Derivatives: From Their Weak Basicity to Their Application in Frustrated Lewis Pair Chemistry

Damien Mahaut; Guillaume Berionni; Benoît Champagne

doi:10.1021/acs.jpca.2c01339

9-Phosphatriptycene Derivatives: From Their Weak Basicity to Their Application in Frustrated Lewis Pair Chemistry

Damien Mahaut, Guillaume Berionni, Benoît Champagne

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

Abstract

The accurate prediction of the basicity of tertiary phosphines in acetonitrile and water is reported by the linear correlation between computed ΔpKa's obtained by density functional theory (DFT) and experimental values extracted from the literature. This method is applied to the prediction of pKa values of 9-phosphatriptycene derivatives and showed that they are weaker Brønsted bases than their triphenylphosphine analogues. This lower reactivity is attributed to their high pyramidalization that increases their lone pair 3s character, stabilizing its energy level. Their potential application in frustrated Lewis pair chemistry is then considered by investigating the hydrogenation of 1,1-diphenylethylene by the tris(pentafluorophenyl)borane/1-chloro-9-phosphatriptycene frustrated Lewis pair.

Original language	English
Pages (from-to)	2794-2801
Number of pages	8
Journal	The Journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory
Volume	126
Issue number	18
DOIs	https://doi.org/10.1021/acs.jpca.2c01339
Publication status	Published - 12 May 2022

Funding

We acknowledge the University of Namur and the Fonds de la Recherche Scientifique-FNRS (F.R.S.-FNRS) (FRIA PhD grant for DM and convention F.4513.18 for GB) for their financial support. The calculations were performed on the computers of the Consortium des E\u0301quipements de Calcul Intensif, particularly those of the High-Performance Computing Platform, which was supported by the FNRS-FRFC, the Walloon Region, and the University of Namur (conventions no. GEQ U.G006.15, U.G018.19, 1610468, and RW/GEQ2016). The PC platform is acknowledged for technical support. We thank Dr. Aure\u0301lien Chardon, Dr. Lei Hu, and Prof. Raphae\u0308l Robiette for useful discussions on the reactivity of 9-phosphatriptycenes.

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10.1021/acs.jpca.2c01339

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title = "9-Phosphatriptycene Derivatives: From Their Weak Basicity to Their Application in Frustrated Lewis Pair Chemistry",

abstract = "The accurate prediction of the basicity of tertiary phosphines in acetonitrile and water is reported by the linear correlation between computed ΔpKa's obtained by density functional theory (DFT) and experimental values extracted from the literature. This method is applied to the prediction of pKa values of 9-phosphatriptycene derivatives and showed that they are weaker Br{\o}nsted bases than their triphenylphosphine analogues. This lower reactivity is attributed to their high pyramidalization that increases their lone pair 3s character, stabilizing its energy level. Their potential application in frustrated Lewis pair chemistry is then considered by investigating the hydrogenation of 1,1-diphenylethylene by the tris(pentafluorophenyl)borane/1-chloro-9-phosphatriptycene frustrated Lewis pair. ",

author = "Damien Mahaut and Guillaume Berionni and Beno{\^i}t Champagne",

note = "Publisher Copyright: {\textcopyright} 2022 American Chemical Society.",

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doi = "10.1021/acs.jpca.2c01339",

language = "English",

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9-Phosphatriptycene Derivatives: From Their Weak Basicity to Their Application in Frustrated Lewis Pair Chemistry. / Mahaut, Damien ; Berionni, Guillaume ; Champagne, Benoît.
In: The Journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, Vol. 126, No. 18, 12.05.2022, p. 2794-2801.

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

TY - JOUR

T1 - 9-Phosphatriptycene Derivatives

T2 - From Their Weak Basicity to Their Application in Frustrated Lewis Pair Chemistry

AU - Mahaut, Damien

AU - Berionni, Guillaume

AU - Champagne, Benoît

PY - 2022/5/12

Y1 - 2022/5/12

N2 - The accurate prediction of the basicity of tertiary phosphines in acetonitrile and water is reported by the linear correlation between computed ΔpKa's obtained by density functional theory (DFT) and experimental values extracted from the literature. This method is applied to the prediction of pKa values of 9-phosphatriptycene derivatives and showed that they are weaker Brønsted bases than their triphenylphosphine analogues. This lower reactivity is attributed to their high pyramidalization that increases their lone pair 3s character, stabilizing its energy level. Their potential application in frustrated Lewis pair chemistry is then considered by investigating the hydrogenation of 1,1-diphenylethylene by the tris(pentafluorophenyl)borane/1-chloro-9-phosphatriptycene frustrated Lewis pair.

AB - The accurate prediction of the basicity of tertiary phosphines in acetonitrile and water is reported by the linear correlation between computed ΔpKa's obtained by density functional theory (DFT) and experimental values extracted from the literature. This method is applied to the prediction of pKa values of 9-phosphatriptycene derivatives and showed that they are weaker Brønsted bases than their triphenylphosphine analogues. This lower reactivity is attributed to their high pyramidalization that increases their lone pair 3s character, stabilizing its energy level. Their potential application in frustrated Lewis pair chemistry is then considered by investigating the hydrogenation of 1,1-diphenylethylene by the tris(pentafluorophenyl)borane/1-chloro-9-phosphatriptycene frustrated Lewis pair.

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DO - 10.1021/acs.jpca.2c01339

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SN - 1089-5639

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JO - The Journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory

JF - The Journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory

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9-Phosphatriptycene Derivatives: From Their Weak Basicity to Their Application in Frustrated Lewis Pair Chemistry

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High Performance Computing Technology Platform

Physical Chemistry and characterization(PC2)

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9-Phosphatriptycene Derivatives: From Their Weak Basicity to Their Application in Frustrated Lewis Pair Chemistry

Abstract

Funding

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High Performance Computing Technology Platform

Physical Chemistry and characterization(PC2)

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