Carbon−Fluorine Bond Hydrogenolysis in Perfluoroethyl−Iridium Complexes To Give HFC-134a Involves Heterolytic Activation of H2

Reaction of Cp*Ir(PMe 3 )(CF 2 CF 3 )H with CH 3 CO 2 D affords mostly Cp*Ir(PMe 3 )(CFHCF 3 )(O 2 CCH 3 ), while the corresponding reaction of Cp*Ir(PMe 3 )(CF 2 CF 3 )D with CH 3 CO 2 H affords mostly Cp*Ir(PMe 3 )(CFDCF 3 )(O 2 CCH 3 ). These results are consistent with external protonation of the CF bond and migration of the originally present H (or D) from Ir to C and suggest that the previously reported CF bond hydrogenolysis using dihydrogen proceeds via heterolytic activation of the H 2 molecule at iridium.