A solvent dependent C(sp3)-CF3 bond-forming reductive elimination from neutral four-coordinate Cu(III) complexes [(L)Cu(CF3)2(CH2CO2tBu)] (L = pyridine or its derivatives) is described. Reactions in less polar solvent ClCH2CH2Cl proceed via a concerted bond breaking/bond forming process along with the reorientation of the ligand, while reaction in polar solvent DMF occurs via a rate limiting ligand-dissociation, followed by C(sp3)-CF3 reductive elimination from the resulting three-coordinate intermediate. These mechanistic proposals are supported by kinetic studies that included ligand and temperature effects, as well as DFT calculations.
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Solvent-Dependent C(sp3)-CF3 Reductive Elimination from Neutral Four-Coordinate Cu(III) Complexes.
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