The synthesis and chemistry of fluorovinyl-containing phosphines and the single crystal X-ray structure of SPPr
i2(CF
CF2)
Abstract
The first perfluorovinyl 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
CF2)
(X = F, Cl) is reacted with LiAlH4 a mixture of PR2(CX
CFH) isomers and other defluorinated materials are produced, but the reaction with LiAlH(OBut)3 affords the single products Z-PR2(CF
CFH) or E-PR2(CCl
CFH), respectively, in high yields. Reaction of the fluorovinyl alkyl phosphines with
CF2) is the first perfluorovinyl phosphorus(V) compound to be characterised crystallographically and it exhibits an unusually short [1.9358(9)
Å] P
S bond. Reaction of fluorovinyl
CF2), identified on the basis of multinuclear
CF2) with Br2 results in bromine addition across the double bond to give OPPh2(CFBrCF2Br).