C−H and C−F Bond Activation Reactions of Fluorinated Propenes at Rhodium: Distinctive Reactivity of the Refrigerant HFO‐1234yf |
| |
| Authors: | Maria Talavera Cortney N von&#x;Hahmann Robert Müller Mike Ahrens Martin Kaupp Thomas Braun |
| |
| Institution: | Maria Talavera,Cortney N. von?Hahmann,Robert Müller,Mike Ahrens,Martin Kaupp,Thomas Braun |
| |
| Abstract: | The reaction of Rh(H)(PEt3)3] ( 1 ) with the refrigerant HFO‐1234yf (2,3,3,3‐tetrafluoropropene) affords an efficient route to obtain Rh(F)(PEt3)3] ( 3 ) by C?F bond activation. Catalytic hydrodefluorinations were achieved in the presence of the silane HSiPh3. 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(CF3)=CHF}(PEt3)3] ( 4 ). Similar rearrangements of HFO‐1234yf were observed at Rh(E)(PEt3)3] E=Bpin ( 6 ), C7D7 ( 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. |
| |
| Keywords: | C-H-Aktivierung Fluor Olefine Rhodium Silane |
|
|
