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C−H and C−F Bond Activation Reactions of Fluorinated Propenes at Rhodium: Distinctive Reactivity of the Refrigerant HFO‐1234yf
Author(s) -
Talavera Maria,
von Hahmann Cortney N.,
Müller Robert,
Ahrens Mike,
Kaupp Martin,
Braun Thomas
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201902872
Subject(s) - reactivity (psychology) , chemistry , silane , rhodium , catalysis , refrigerant , fluorine , medicinal chemistry , polymer chemistry , stereochemistry , organic chemistry , thermodynamics , medicine , physics , alternative medicine , pathology , gas compressor
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.