C−H and C−F Bond Activation Reactions of Fluorinated Propenes at Rhodium: Distinctive Reactivity of the Refrigerant HFO-1234yf
Dr. Maria Talavera
Department of Chemistry, Humboldt Universität zu Berlin, Brook-Taylor-Strasse 2, 12489 Berlin, Germany
These authors contributed equally to this work.
Search for more papers by this authorCortney N. von Hahmann
Department of Chemistry, Humboldt Universität zu Berlin, Brook-Taylor-Strasse 2, 12489 Berlin, Germany
These authors contributed equally to this work.
Search for more papers by this authorDr. Robert Müller
Institut für Chemie, Theoretische Chemie/Quantenchemie, Sekr. C7, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin, Germany
Search for more papers by this authorDr. Mike Ahrens
Department of Chemistry, Humboldt Universität zu Berlin, Brook-Taylor-Strasse 2, 12489 Berlin, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Martin Kaupp
Institut für Chemie, Theoretische Chemie/Quantenchemie, Sekr. C7, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Thomas Braun
Department of Chemistry, Humboldt Universität zu Berlin, Brook-Taylor-Strasse 2, 12489 Berlin, Germany
Search for more papers by this authorDr. Maria Talavera
Department of Chemistry, Humboldt Universität zu Berlin, Brook-Taylor-Strasse 2, 12489 Berlin, Germany
These authors contributed equally to this work.
Search for more papers by this authorCortney N. von Hahmann
Department of Chemistry, Humboldt Universität zu Berlin, Brook-Taylor-Strasse 2, 12489 Berlin, Germany
These authors contributed equally to this work.
Search for more papers by this authorDr. Robert Müller
Institut für Chemie, Theoretische Chemie/Quantenchemie, Sekr. C7, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin, Germany
Search for more papers by this authorDr. Mike Ahrens
Department of Chemistry, Humboldt Universität zu Berlin, Brook-Taylor-Strasse 2, 12489 Berlin, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Martin Kaupp
Institut für Chemie, Theoretische Chemie/Quantenchemie, Sekr. C7, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Thomas Braun
Department of Chemistry, Humboldt Universität zu Berlin, Brook-Taylor-Strasse 2, 12489 Berlin, Germany
Search for more papers by this authorDedicated to Professor Helmut Werner on the occasion of his 85th birthday
Graphical Abstract
Cool down: Using the refrigerant HFO-1234yf together with [RhH(PEt3)3], a C−F bond activation occurs to produce a rhodium fluorido complex. This reaction is followed by a C−H bond activation mediated by the fluorosilane and a subsequent 1,2-fluorine shift.
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.
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