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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 | 2021 Aug

REPOSITORIES: biostudies-literature

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

Talavera Maria M   Braun Thomas T  

Chemistry (Weinheim an der Bergstrasse, Germany) 20210628 46

The reaction of the rhodium(I) complexes [Rh(E)(PEt<sub>3</sub> )<sub>3</sub> ] (E=GePh<sub>3</sub> (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<sub>3</sub> CHCF<sub>2</sub> )(PEt<sub>3</sub> )<sub>2</sub> ] (2) together with the fluorophosphorane E-(CF<sub>3</sub> )CH=CF(PFEt<sub>3</sub> ). For [Rh(Si(OEt)<sub>3</sub> )(PEt<sub>3</sub> )<sub>3</sub> ] (4  ...[more]

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