Stepwise Reduction of an α-Phosphonio-Carbocation to a Crystalline Phosphorus Radical Cation and an Acridinyl-Phosphorus Ylide

We have synthesized the dicationic α‐phosphonio–carbocation 12+, which can be regarded as a two‐electron oxidized phosphorus ylide. Carbocation 12+ exhibits two reversible reduction waves at −0.28 and −0.90 V (vs. Fc+/Fc) indicating that both the radical cation 1.+ and the neural phosphorus ylide 1...

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Published inChemistry : a European journal Vol. 22; no. 9; pp. 2882 - 2886
Main Authors Hudnall, Todd W., Dorsey, Christopher L., Jones, James S., Gabbaï, François P.
Format Journal Article
LanguageEnglish
Published WEINHEIM Blackwell Publishing Ltd 24.02.2016
Wiley
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Summary:We have synthesized the dicationic α‐phosphonio–carbocation 12+, which can be regarded as a two‐electron oxidized phosphorus ylide. Carbocation 12+ exhibits two reversible reduction waves at −0.28 and −0.90 V (vs. Fc+/Fc) indicating that both the radical cation 1.+ and the neural phosphorus ylide 1 can be generated. Indeed, reduction of 12+ with Zn afforded 1.+ as a dark green solid that was characterized by XRD and EPR spectroscopy, and reduction with Mg(Ant)⋅(THF)3 gave 1, which was characterized by 1H and 31P NMR spectroscopy. Computational analyses reveal the stepwise population of a C−P π bonding orbital upon reduction of 12+. The first synthesized α‐phosphonio–carbocation undergoes one‐electron reduction to afford a stable radical cation that features a one‐electron P−C π bond (see picture) and two‐electron reduction to the corresponding antiaromatic phosphorus ylide.
Bibliography:ArticleID:CHEM201504744
Welch Foundation - No. A-1423
American Chemical Society-PRF - No. 54584-UR3
ark:/67375/WNG-8ZPQSXR2-4
Texas A&M University
istex:D96E5A42DE410E6FD73D7159BED28833178D3C00
National Science Foundation - No. CHE-1362140; No. CHE-0821254; No. CHE-0946998; No. CHE-1300371
Laboratory for Molecular Simulation at Texas A&M University
National Science Foundation
ObjectType-Article-1
SourceType-Scholarly Journals-1
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ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201504744