C−H and C−F Bond Activation Reactions of Fluorinated Propenes at Rhodium: Distinctive Reactivity of the Refrigerant HFO‐1234yf

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The reaction of [Rh(H)(PEt 3 ) 3 ] ( 1 ) with the refrigerant HFO‐1234yf (2,3,3,3‐tetrafluoropropene) affords an efficient route to obtain [Rh(F)(PEt 3 ) 3 ] ( 3 ) by C−F bond activation. Catalytic hydrodefluorinations were achieved in the presence of the silane HSiPh 3 . In the presence of a fluorosilane, 3 provides a C−H bond activation followed by a 1,2‐fluorine shift to produce [Rh{( E )‐C(CF 3 )=CHF}(PEt 3 ) 3 ] ( 4 ). Similar rearrangements of HFO‐1234yf were observed at [Rh(E)(PEt 3 ) 3 ] [E=Bpin ( 6 ), C 7 D 7 ( 8 ), Me ( 9 )]. The ability to favor C−H bond activation using 3 and fluorosilane is also demonstrated with 3,3,3‐trifluoropropene. Studies are supported by DFT calculations.