Versatile Reaction Pathways of 1,1,3,3,3‐Pentafluoropropene at Rh(I) Complexes [Rh(E)(PEt(3))(3)] (E=H, GePh(3), Si(OEt)(3), F, Cl): C‐F versus C‐H Bond Activation Steps

The reaction of the rhodium(I) complexes [Rh(E)(PEt(3))(3)] (E=GePh(3) (1), H (6), F (7)) with 1,1,3,3,3‐pentafluoropropene afforded the defluorinative germylation products Z/E‐2‐(triphenylgermyl)‐1,3,3,3‐tetrafluoropropene and the fluorido complex [Rh(F)(CF(3)CHCF(2))(PEt(3))(2)] (2) together with the fluorophosphorane E‐(CF(3))CH=CF(PFEt(3)). For [Rh(Si(OEt)(3))(PEt(3))(3)] (4) the coordination of the fluoroolefin was found to give [Rh{Si(OEt)(3)}(CF(3)CHCF(2))(PEt(3))(2)] (5). Two equivalents of complex 2 reacted further by C−F bond oxidative addition to yield [Rh(CF=CHCF(3))(PEt(3))(2)(μ‐F)(3)Rh(CF(3)CHCF(2))(PEt(3))] (9). The role of the fluorido ligand on the reactivity of complex 2 was assessed by comparison with the analogous chlorido complex. The use of complexes 1, 4 and 6 as catalysts for the derivatization of 1,1,3,3,3‐pentafluoropropene provided products, which were generated by hydrodefluorination, hydrometallation and germylation reactions.