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

机译:C-H和C-F键活化反应在RHODIUM(RHODIUM)的氟化物:制冷剂HFO-1234YF的独特反应性

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摘要

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.
机译:[RH(H)(PET3)](3)的反应与制冷剂HFO-1234YF(2,3,3,3-四氟丙烯)提供有效的途径以获得[RH(F)(PET3)( 3)](3)通过CF键活化。 在硅烷HSIPH3存在下实现催化加氢氟化珠。 在氟硅烷的存在下,3提供C-H键活化,然后提供1,2-氟变换,以产生[RH {(E)-C(CF3)= CHF}(PET3)(3)](4)。 在[RH(e)(PET3)(3)] [E = BPIN(6),C7D7(8),ME(9)],观察到相似的HFO-1234YF的重排。 使用3,3,3-三氟丙烯还证明了最有利于3和氟硅烷的C-H键活化的能力。 DFT计算支持研究。

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