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Issue 3, 1999
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Synthesis and co-ordination chemistry of perfluorovinyl phosphine derivatives. Single crystal structures of PPh(CF[double bond, length half m-dash]CF2)2, cis-[PtCl2{PPh2(CF[double bond, length half m-dash]CF2)}2] and [{AuCl[PPh2(CF[double bond, length half m-dash]CF2)]}2]

Abstract

Reaction of perfluorovinyllithium, derived from CF3CH2F, with chloro-substituted phosphines generated perfluorovinylphosphines of the type PPhm(CF[double bond, length half m-dash]CF2)n and P(CF[double bond, length half m-dash]CF2)nClm (n + m = 3) in high yields. A low-temperature crystal structure determination of the air- and moisture-stable compound PPh(CF=CF2)2 provided the first reported structural data for any perfluorovinyl-containing material. There is considerable variation in the C–F bond distances [1.310(4), 1.321(4), 1.353(3) Å] within the perfluorovinyl group in the phosphine. The co-ordination chemistry of these ligands has been investigated via the synthesis of examples of late transition-metal complexes. The results of single crystal structural determinations of cis-[PtCl2{PPh2(CF[double bond, length half m-dash]CF2)}2] and [{AuCl[PPh2(CF[double bond, length half m-dash]CF2)]}2]·0.5CH2Cl2 are reported. In both of these molecules short metal–phosphorus distances [d(Pt–P)av = 2.231(3) and d(Au–P)av = 2.217(2) Å] are observed compared with typical distances for similar phosphine complexes. A comparison of the electronic properties of these ligands with those of other phosphines, halogenophosphines and phosphites was made on the basis of a spectroscopic investigation of the carbonyl stretching frequencies of the complexes [Mo(CO)5{PPhm(CF[double bond, length half m-dash]CF2)n}] (n + m = 3).

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Supplementary files


Article type: Paper
DOI: 10.1039/A806535G
Citation: J. Chem. Soc., Dalton Trans., 1999,0, 427-434
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    Synthesis and co-ordination chemistry of perfluorovinyl phosphine derivatives. Single crystal structures of PPh(CF[double bond, length half m-dash]CF2)2, cis-[PtCl2{PPh2(CF[double bond, length half m-dash]CF2)}2] and [{AuCl[PPh2(CF[double bond, length half m-dash]CF2)]}2]

    K. K. Banger, R. P. Banham, A. K. Brisdon, W. I. Cross, G. Damant, S. Parsons, R. G. Pritchard and A. Sousa-Pedrares, J. Chem. Soc., Dalton Trans., 1999, 0, 427
    DOI: 10.1039/A806535G

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