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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.

chemistry – a european journal

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