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. Issue 46 (28th June 2021)

• Record Type: Journal Article
• Authors: Talavera, Maria; Braun, Thomas
• Is Part Of: Chemistry. Volume 27:Issue 46(2021)
• Page Start: 11926
• Page End: 11934
• Publication Date: 2021-06-28
• Subjects: C−F bond activation -- fluorine -- fluorido complexes -- germylation -- rhodium; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202101508
• Languages: English
• ISSNs: 0947-6539

Abstract

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. Abstract : Studies on the reactivity of 1, 3, 3, 3‐pentafluoropropene towards rhodium(I) complexes revealed versatile reaction pathways, such as coordination, C−F and C−H bond activation steps. Fluorido ligands play a key role for the reactivity pattern observed.