Perfluoropropenyl-containing phosphines from HFC replacements

A series of new perfluoropropenyl-containing phosphines of the type R3-nP(E-CF=CFCF3)(n) (R = Ph, iPr, n = 1, 2; R = tBu, n = 2) have been prepared from the reaction of the hydrofluoroolefin Z-CF3CF=CFH (HFO-1225ye) with base and the appropriate chlorophosphine, while reaction with Cl2PCH2CH2PCl2 gave (CF(3)CFvCF)(2)PCH2CH2P(CF=CFCF3)(2), the first example of a bidentate perfluoroalkenyl-containing phosphine. An alternative route to these phosphines based on the room- or low-temperature deprotonation of CF3CF2CH2F (HFC-236ea) gives mainly the E-isomer, but also a small amount of the Z-isomer, the ratio of which depends on the reaction temperature. All of the phosphines could be readily oxidised with either H2O2 or urea center dot H2O2, and the phosphine selenides R3-nP(Se)(E-CF=CFCF3)(n) (R = Ph, n = 1,2; R = iPr, n = 1; R = tBu, n = 2) were also prepared. The steric and electronic properties of these ligands were determined based on their platinum(II), palladium(II) and molybdenum carbonyl complexes. The crystal structures of (CF3CF=CF)(2)PCH2CH2P(CF=CFCF3)(2), (CF3CF=CF)(2)P(O)CH2CH2P(O)(CF=CFCF3)(2), iPr(2)P(Se)-(CF=CFCF3)(2), trans-[PtCl2{Ph(3-n)P(E-CF=CFCF3)(n)}(2)] (n = 1 or 2), trans-[PdCl2{R2P(E-CF=CFCF3)}(2)] (R = Ph, iPr) and [Mo(CO)(4){(CF3CF=CF)(2)PCH2CH2P(CF=CFCF3)(2)}] are reported.