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Abstract Herein, we describe the trifluoro‐ and difluoroethoxylation of C(sp2)‐H bonds using nickel(II) complexes incorporating a model macrocyclic arene substrate. Due to the coordinative properties of the macrocyclic substrate, we were able to detect and characterize the just‐formed C(sp2)−OCH2CF3−Ni(II) species by HRMS and IRPD. DFT studies on the C(sp2)−OCH2CF3 bond formation mechanism indicate that it involves a Ni(III)/Ni(I) reductive elimination followed by oxidation to Ni(II) rather than the higher energy barrier Ni(IV)/Ni(II) reductive elimination. This mechanistic investigation deepens the versatile redox abilities of Ni compounds and might help in designing new catalysts for the 2,2,2‐trifluoroethoxylation and 2,2‐difluoroethoxylation of arene C−H bonds.