Perfluoropropenyl-containing phosphines from HFC replacements†
Abstract
A series of new perfluoropropenyl-containing phosphines of the type R3−nP(E-CFCFCF3)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 (CF3CF
CF)2PCH2CH2P(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·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)2PCH2CH2P(CF
CFCF3)2, (CF3CF
CF)2P(O)CH2CH2P(O)(CF
CFCF3)2, iPr2P(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)2PCH2CH2P(CF
CFCF3)2}] are reported.
- This article is part of the themed collection: Fluorine