Additions of PH₃ to Monosubstituted Alkenes of the Formula H₂CCH(CH₂)_x(CF₂)_yCF₃:  Convenient, Multigram Syntheses of a Family of Partially Fluorinated Trialkylphosphines with Modulated Electronic Properties and Fluorous Phase Affinities

Abstract

Reactions of PH(3) and commercially available H(2)C=CHR(f) (R(f6)(/)(8)(/)(10) = (CF(2))(5)CF(3)/(CF(2))(7)CF(3)/(CF(2))(9)CF(3)) give, in two-stage processes conducted with free radical initiators (AIBN, VAZO; 80-90 degrees C), the phosphines P(CH(2)CH(2)R(f))(3) (1-3; 63-75%). Analogous reactions with H(2)C=CHCH(2)R(f8) (7) and H(2)C=CHCH(2)CH(2)R(f8) (10) give P(CH(2)CH(2)CH(2)R(f8))(3) (4, 73%) and P(CH(2)CH(2)CH(2)CH(2)R(f8))(3) (5, 66%), in which the phosphorus is increasingly insulated from the electronegative R(f) moiety. The alkenes 7 and 10 are prepared from Bu(3)SnCH(2)CH=CH(2) and IR(f8) (hnu, CH(2)Cl(2), 81%) or ICH(2)R(f8) (VAZO, refluxing CF(3)C(6)H(5), 56%). The reaction of 1 and H(2)O(2) gives O=P(CH(2)CH(2)R(f6))(3) (6, 88%), which can be reduced with HSiCl(3) to 1. Partition coefficients (CF(3)C(6)F(11)/toluene, 27 degrees C) range from 98.8:1.2 (1, 4) through 98.9:1.1 (5) to >99.7:<0.3 (2, 3, 6). Crystals of 4 diffract poorly, but a packing motif that maximizes interactions between R(f) segments is evident.

Enantioselective Catalysis in Fluorinated Media – Synthesis and Properties of Chiral Perfluoroalkylated (Salen)manganese Complexes

“…[2f, 25] With chiral manganese complexes 3 and 4 on hand, we high enantioselectivity levels reported by Mukaiyama and co-workers point to the participation of the metal comwere able to study the feasibility of enantioselective catalytic reactions under FBS conditions. Among the manifold oxid-plexes in the oxygen transfer.…”

Thermoregulated Liquid/Liquid Catalyst Separation and Recycling

“…After completion of the reaction the products can be easily removed from the catalyst by cooling the mixture again and separating the layers. [6][7][8][9][10][11][12] In analogy to this concept, similar work has been done using carbon dioxide partial pressures up to 6 MPa or supercritical carbon dioxide instead of increased temperatures to homogenise the fluorous and the organic phase. This homogenisation is reversible by releasing the CO 2 pressure.…”

Perfluorinated oxygen- and sulfur-containing compounds as extractants for gold(III)

“…The fluorous chains give a "T" shape to the molecule and the packing is such that fluorous-fluorous interactions are maximised. The packing motif is similar to that of the phosphine P(CH 2 CH 2 CH 2 (CF 2 ) 7 CF 3 ) 3 [11]. Additional interactions between the oxygen and hydrogen of a second molecule are also present that form infinite stacks along the P=O vector.…”

“…This has led to a plethora of ligands designed for homogeneous catalysis, the majority of which are based on modifications of tertiary phosphines [7][8][9]. Whilst perfluoroalkyl and aryl phosphines have been examined, the corresponding perfluorophosphine oxides have only briefly been described in the literature as intermediates in the synthesis of the phosphines [10,11], and no coordination chemistry has been reported. We have been investigating the use of these perfluorinated analogues of TOPO for extraction of a number of metals and radioisotopes from water into fluorinated solvents [12,13], and the use of perfluorinated phenols for the removal of a number of radionuclides from water [14].…”