C–F activation of 2,3,5,6-tetrafluoropyridine at [Rh{Si(OEt)3}(PEt3)3] (1) yields [Rh{2-(3,5,6-C5F3HN)}(PEt3)3] (2) and FSi(OEt)3, but in an unprecedented consecutive reaction FSi(OEt)3 acts as a fluoride source to give [Rh(4-C5F4N)(PEt3)3] (4) by regeneration of the C–F bond and C–H activation. Analogous refluorination steps were observed for other 2-pyridyl rhodium complexes. NMR spectroscopic studies revealed a delicate balance between the feasibility for C–F bond formation accompanied by a C–H activation and the occurrence of competing reactions such as hydrodefluorinations induced by the intermediary presence of H2.
