| How Lewis acidic is your cation? Putting phosphenium ions on the fluoride ion affinity scale. | |
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MedLine Citation:
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PMID: 22159000 Owner: NLM Status: Publisher |
Abstract/OtherAbstract:
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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 [Me(3)C](+) or [Me(3)Si](+). 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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Authors:
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John M Slattery; Sharifa Hussein |
Publication Detail:
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Type: JOURNAL ARTICLE Date: 2011-12-13 |
Journal Detail:
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Title: Dalton transactions (Cambridge, England : 2003) Volume: - ISSN: 1477-9234 ISO Abbreviation: - Publication Date: 2011 Dec |
Date Detail:
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Created Date: 2011-12-13 Completed Date: - Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 101176026 Medline TA: Dalton Trans Country: - |
Other Details:
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Languages: ENG Pagination: - Citation Subset: - |
Affiliation:
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Department of Chemistry, University of York, Heslington, York, UKYO10 5DD. john.slattery@york.ac.uk. |
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From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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