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Versatile Reaction Pathways of 1,1,3,3,3-Pentafluoropropene at Rh(I) Complexes [Rh(E)(PEt₃ )₃ ] (E=H, GePh₃ , Si(OEt)₃ , F, Cl): C-F versus C-H Bond Activation Steps.

ABSTRACT: The reaction of the rhodium(I) complexes [Rh(E)(PEt₃ )₃ ] (E=GePh₃ (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)(CF₃ CHCF₂ )(PEt₃ )₂ ] (2) together with the fluorophosphorane E-(CF₃ )CH=CF(PFEt₃ ). For [Rh(Si(OEt)₃ )(PEt₃ )₃ ] (4) the coordination of the fluoroolefin was found to give [Rh{Si(OEt)₃ }(CF₃ CHCF₂ )(PEt₃ )₂ ] (5). Two equivalents of complex 2 reacted further by C-F bond oxidative addition to yield [Rh(CF=CHCF₃ )(PEt₃ )₂ (μ-F)₃ Rh(CF₃ CHCF₂ )(PEt₃ )] (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.

SUBMITTER: Talavera M

PROVIDER: S-EPMC8456946 | biostudies-literature |

REPOSITORIES: biostudies-literature

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