How Lewis acidic is your cation? Putting phosphenium ions on the fluoride ion affinity scale

John M. Slattery; Sharifa Hussein

doi:10.1039/c1dt11636c

How Lewis acidic is your cation? Putting phosphenium ions on the fluoride ion affinity scale

John M. Slattery, Sharifa Hussein

Chemistry

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

Abstract

The fluoride ion affinities (FIAs) of 33 phosphenium ions with a range of substituents were calculated using ab inito and DFT methods. The use of these FIA data as a measure of the Lewis acidities of phosphenium ions is described and the FIAs of the species studied here are compared to FIA data for more commonly encountered Lewis acids. Phosphenium ions are often stronger Lewis acids than neutral species, but in many cases are less Lewis acidic than highly electrophilic cations such as [Me3C](+) or [Me3Si](+). The impact of mesomeric, inductive and steric substituent effects on FIAs are discussed and related to the underlying electronic structures of different cation types. A comparison between the FIAs of known "free" phosphenium ions with those that are currently unknown and other highly electrophilic cations suggests that some diaryl- and dialkylphosphenium ions may yet be accessible under the right conditions.

Original language	English
Pages (from-to)	1808-1815
Number of pages	8
Journal	Dalton Transactions
Volume	41
Issue number	6
DOIs	https://doi.org/10.1039/c1dt11636c
Publication status	Published - 14 Feb 2012

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10.1039/c1dt11636c

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AB - The fluoride ion affinities (FIAs) of 33 phosphenium ions with a range of substituents were calculated using ab inito and DFT methods. The use of these FIA data as a measure of the Lewis acidities of phosphenium ions is described and the FIAs of the species studied here are compared to FIA data for more commonly encountered Lewis acids. Phosphenium ions are often stronger Lewis acids than neutral species, but in many cases are less Lewis acidic than highly electrophilic cations such as [Me3C](+) or [Me3Si](+). The impact of mesomeric, inductive and steric substituent effects on FIAs are discussed and related to the underlying electronic structures of different cation types. A comparison between the FIAs of known "free" phosphenium ions with those that are currently unknown and other highly electrophilic cations suggests that some diaryl- and dialkylphosphenium ions may yet be accessible under the right conditions.

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How Lewis acidic is your cation? Putting phosphenium ions on the fluoride ion affinity scale

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New Ruthenium Catalysts for C-C bond Formation: A Combined Experimantal and Theoretical Approach

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How Lewis acidic is your cation? Putting phosphenium ions on the fluoride ion affinity scale

Abstract

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New Ruthenium Catalysts for C-C bond Formation: A Combined Experimantal and Theoretical Approach

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