Synthesis and co-ordination chemistry of perfluorovinyl phosphine derivatives. Single crystal structures of PPh(CF=CF2)(2), cis-[PtCl2{PPh2(CF=CF2)}(2)] and [{AuCl[PPh2(CF=CF2)]}(2)]

Reaction of perfluorovinyllithium, derived from CF3CH2F, with chloro-substi tuted phosphines generated perfluorovinylphosphines of the type PPhm(CF=CF2 )(n) and P(CF=CF2)(n)Cl-m (n + m = 3) in high yields. A low-temperature cry stal structure determination of the air- and moisture-stable compound PPh(C F=CF2)(2) provided the first reported structural data for any perfluoroviny l-containing material. There is considerable variation in the C-F bond dist ances [1.310(4), 1.321(4), 1.353(3) Angstrom] within the perfluorovinyl gro up in the phosphine. The co-ordination chemistry of these ligands has been investigated via the synthesis of examples of late transition-metal complex es. The results of single crystal structural determinations of cis-[PtCl2{P Ph2(CF=CF2)}(2)] and [{AuCl[PPh2(CF=CF2)]}(2)]. 0.5CH(2)Cl(2) 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) Angstrom] are observed compared with t ypical distances for similar phosphine complexes. A comparison of the elect ronic properties of these ligands with those of other phosphines, halogenop hosphines and phosphites was made on the basis of a spectroscopic investiga tion of the carbonyl stretching frequencies of the complexes [Mo(CO)(5){PPh m(CF=CF2)(n)}] (n + m = 3).