Publication Date:
2013-09-21
Description:
Prototypical Lewis acids, such as boranes, derive their reactivity from electronic unsaturation. Here, we report the Lewis acidity and catalytic application of electronically saturated phosphorus-centered electrophilic acceptors. Organofluorophosphonium salts of the formula [(C6F5)(3-x)Ph(x)PF][B(C6F5)4] (x = 0 or 1; Ph, phenyl) are shown to form adducts with neutral Lewis bases and to react rapidly with fluoroalkanes to produce difluorophosphoranes. In the presence of hydrosilane, the cation [(C6F5)3PF](+) is shown to catalyze the hydrodefluorination of fluoroalkanes, affording alkanes and fluorosilane. The mechanism demonstrates the impressive fluoride ion affinity of this highly electron-deficient phosphonium center.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Caputo, Christopher B -- Hounjet, Lindsay J -- Dobrovetsky, Roman -- Stephan, Douglas W -- New York, N.Y. -- Science. 2013 Sep 20;341(6152):1374-7. doi: 10.1126/science.1241764.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6, Canada.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/24052304" target="_blank"〉PubMed〈/a〉
Print ISSN:
0036-8075
Electronic ISSN:
1095-9203
Topics:
Biology
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Chemistry and Pharmacology
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Computer Science
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Medicine
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Natural Sciences in General
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Physics
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