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C-F activation of 2,3,5,6-tetrafluoropyridine at [Rh{Si(OEt) 3 }(PEt 3 ) 3 ] ( 1 ) yields [Rh{2-(3,5,6-C 5 F 3 HN)}(PEt 3 ) 3 ] ( 2 ) and FSi(OEt) 3 , but in an unprecedented consecutive reaction FSi(OEt) 3 acts as a fluoride source to give [Rh(4-C 5 F 4 N)(PEt 3 ) 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 H 2 .

Consecutive C–F bond activation and C–F bond formation of heteroaromatics at rhodium: the peculiar role of FSi(OEt)3

Consecutive C–F bond activation and C–F bond formation of heteroaromatics at rhodium: the peculiar role of FSi(OEt)₃