Reaction of [RhH (PEt3) 4](9) with hexafluoropropene (1) affords the C–F activation product [Rh {(Z)-CFCF (CF3)}(PEt3) 3](4) as well as Et3P (F){(Z)-CFCF (CF3)}(11). In contrast, addition of (E)-1, 2, 3, 3, 3-pentafluoropropene (8) to 9 yields [Rh {(E)-C (CF3) CHF}(PEt3) 3](12) together with [RhF (PEt3) 3](6) and (Z)-1, 3, 3, 3-tetrafluoropropene (10). Treatment of 12 with hydrogen effects the formation of 1, 1, 1-trifluoropropane (2) and the fluoro ...