Abstract
The reaction of tetrachlorodiphosphines [Cl2 P(CH2 )n PCl2 ;
n = 2-4] with fluorous
aromatic precursors 4-bromo(perfluorohexyl)benzene and 4-(perfluorohexyl)phenol
gave a series of fluorous-tagged diphosphines [(p -C6 F13 C6 H4 )2 P(CH2 )n P(C6 H4 C6 F13 -p )2 ; n = 2-4] and
a new diphosphonite [(p -C6 F13 C6 H4 O)2 P(CH2 )3 P(OC6 H4 C6 F13 -p )2 ]. The improved
synthesis of 1,3-bis(dichlorophosphino)propane (dcpp), involved
the facile chlorination of the corresponding primary phosphine with
triphosgene. Fluorinated diimines RN=C(CH3 )C(CH3 )=NR,
where R = p -C6 H4 C6 F13 or p -C6 H4 C8 F17 have
also been prepared, and were found to be air-stable alternatives to
the highly air-sensitive phosphorus-containing ligands. All compounds
were characterised by a variety of techniques including NMR, IR,
MS and microanalysis. The successful reduction of the phosphine-oxides [(p -C6 F13 C6 H4 )2 P(O)(CH2 )n P(O)(C6 H4 C6 F13 -p )2 ; n = 2,3] with
phenylsilane is also presented.
Key words
fluorous phosphine - scCO2 catalysis - supercritical
fluids - copper coupling
