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Issue 7, 2004
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The synthesis and chemistry of fluorovinyl-containing phosphines and the single crystal X-ray structure of SPPri2(CF[double bond, length as m-dash]CF2)

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Abstract

The first perfluorovinyl alkyl-containing phosphines of the type PR2(CF[double bond, length as m-dash]CF2) (R = Et, iPr, Cy) are reported. The reactivity of these air- and moisture-stable materials has been explored, both at the phosphorus centre and at the fluorovinyl moiety. When PR2(CX[double bond, length as m-dash]CF2) (X = F, Cl) is reacted with LiAlH4 a mixture of PR2(CX[double bond, length as m-dash]CFH) isomers and other defluorinated materials are produced, but the reaction with LiAlH(OBut)3 affords the single products Z-PR2(CF[double bond, length as m-dash]CFH) or E-PR2(CCl[double bond, length as m-dash]CFH), respectively, in high yields. Reaction of the fluorovinyl alkyl phosphines with hydrogen peroxide, elemental sulfur or selenium yields fluorovinyl-containing phosphine oxides, sulfides and selenides, respectively. The phosphine sulfide SPPri2(CF[double bond, length as m-dash]CF2) is the first perfluorovinyl phosphorus(V) compound to be characterised crystallographically and it exhibits an unusually short [1.9358(9) Å] P[double bond, length as m-dash]S bond. Reaction of fluorovinyl phosphines with XeF2 results in compounds of the type F2PR2(CF[double bond, length as m-dash]CF2), identified on the basis of multinuclear NMR studies. These compounds decompose in the presence of moisture to yield the respective phosphine oxides. Reaction of OPPh2(CF[double bond, length as m-dash]CF2) with Br2 results in bromine addition across the double bond to give OPPh2(CFBrCF2Br).

Graphical abstract: The synthesis and chemistry of fluorovinyl-containing phosphines and the single crystal X-ray structure of SPPri2(CF [[double bond, length as m-dash]] CF2)

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Publication details

The article was received on 09 Dec 2003, accepted on 24 Feb 2004 and first published on 09 Jun 2004


Article type: Paper
DOI: 10.1039/B316099H
Citation: New J. Chem., 2004,28, 828-837
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    The synthesis and chemistry of fluorovinyl-containing phosphines and the single crystal X-ray structure of SPPri2(CF[double bond, length as m-dash]CF2)

    N. A. Barnes, A. K. Brisdon, F. R. W. Brown, W. I. Cross, I. R. Crossley, C. Fish, J. V. Morey, R. G. Pritchard and L. Sekhri, New J. Chem., 2004, 28, 828
    DOI: 10.1039/B316099H

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