Hydrodefluorination of pentafluoropyridine at rhodium using dihydrogen: detection of unusual rhodium hydrido complexes.

The pentafluoropyridyl complex [Rh(4-C5NF4)(PEt3)3] (3) reacts with H2 to give initially the dihydrido complex cis-mer-[Rh(H)2(4-C5NF4)(PEt3)3] (6). Within a few hours 2,3,5,6-tetrafluoropyridine as well as two rhodium(III) complexes mer-[Rh(H)3(PEt3)3] (mer-) and fac-[Rh(H)3(PEt3)3] (fac-) are formed. A catalytic C-F activation process for the formation of 2,3,5,6-tetrafluoropyridine starting from pentafluoropyridine and dihydrogen using 3 as a catalyst has been developed.