Reactivity of rhodium hydrido and silyl complexes towards 1,1-difluoroallene

[Display omitted] •Unusual reactions of 1,1,-difluoroallene towards rhodium complexes are described.•Coordination and insertion into RhH or RhSi bonds were observed as supported by NMR spectroscopy, X-ray crystallographyand DFT calculations.•Surprisingly, with hexafluoropropene metallacyclopropane formation and no C-F activation occurred. The reaction of rhodium(I) complexes [Rh(E)(PEt3)3] (E = H (2), Si(OEt)3 (4)) with 1,1-difluoroallene provides the rhodium (III) complexes [Rh(η2-CH2CCF2)(η3-CH2C(E)CF2)(PEt3)2] (E = H (3), Si(OEt)3 (5)). The conversions involve the coordination of one equivalent of difluoroallene to form a rhodiumcyclopropane and the insertion of a second equivalent into the Rh-E bond. X-ray crystallography as well as DFT calculations support the suggested structures as well as the arrangement of the fluorinated ligands. In contrast, when [Rh{Si(OEt)3}(PEt3)3] (4) reacted with hexafluoropropene, only the coordination of the fluorinated olefin was observed resulting in the formation of [Rh(CF2CFCF3){Si(OEt)3}(PEt3)2] (6).