Keywords: fluoroakynyl | fluoroalkenyl | fluoroalkyl | phosphines | methodology | metal complexes | catalysis.
A major theme of our research concentrates on making new organofluorine-containing phosphorus(III) systems because such ligands show a unique combination of steric and electronic properties, often along with enhanced thermal and oxidative stability, suitable for catalytic applications.
In addition to the HFC routes described above (eg to give PR2(CF=CF2), PR2(CCl=CF2), PR2(CF=CFH), PR(CCCF3)2 etc.) We have developed a generic method for introducing fluoroalkyl ligands into phosphines, to give new fluoroalkyl-containing phosphines, such as Ph2P(i-C3F7), shown below, which is the first reported phospine containing a secondary fluoroalkyl group. We have also reported perfluoro- t-Bu, Cy and many other sterically demanding electron-withdrawing groups.
By modifying the fluorinated group we can change the steric and electronic effects at the phosphorus centre and so modify the ligand's properties, and this we study via coordination chemistry and spectroscopy. We also prepare main-group and transition-metal systems containing these ligands and investigate their applications in catalysis.
We have also investigated new synthetic routes to fluoro-phosphites, and related compounds; again these can be used as ligands which we can readily modify the steric, electronic and solvency effects, and generated unusual packing motifs for inorganic systems.