Carbon-carbon bond-forming reductive elimination from elusive organocopper(III) complexes has been considered the key step in many copper-catalyzed and organocuprate reactions. However, organocopper(III) complexes with well-defined structures that can undergo reductive elimination are extremely rare, especially for the formation of Csp 3-Csp 3 bonds. We report herein a general method for the synthesis of a series [alkyl-Cu III-(CF 3) 3 ]complexes, the structures of which have been unequivocally characterized by NMR, mass spectrometry and X-ray crystal diffraction. At elevated temperature, these complexes undergo reductive elimination following first-order kinetics, forming alky-CF 3 products with good yields (up to 91%). Both Kinetic studies and DFT calculations indicate that the reductive elimination to form Csp 3-CF 3 bonds proceeds through a concerted transition state, with a ΔH ‡ =20 kcal/mol barrier.

Capped chelating organic molecules are presented as a design principle for tuning heterogeneous nanoparticles for electrochemical catalysis. Gold nanoparticles (AuNPs) functionalized with a chelating tetradentate porphyrin ligand show a 110-fold enhancement compared to the oleylamine-coated AuNP in current density for electrochemical reduction of CO to CO in water at an overpotential of 340 mV with Faradaic efficiencies (FEs) of 93 %. These catalysts also show excellent stability without deactivation (<5 % productivity loss) within 72 hours of electrolysis. DFT calculation results further confirm the chelation effect in stabilizing molecule/NP interface and tailoring catalytic activity. This general approach is thus anticipated to be complementary to current NP catalyst design approaches.

We report herein a highly efficient Cucatalyzed protocol for the conversion of aliphatic carboxylic acids to the corresponding difluoromethylated analogues. This robust, operationally simple and scalable protocol tolerates a variety of functional groups and can convert a diverse array of acid-containing complex molecules to the alkyl-CF 2 H products. Mechanistic studies support the involvement of alkyl radicals.

Capped chelating organic molecules are presented as a design principle for tuning heterogeneous nanoparticles for electrochemical catalysis. Gold nanoparticles (AuNPs) functionalized with a chelating tetradentate porphyrin ligand show a 110‐fold enhancement compared to the oleylamine‐coated AuNP in current density for electrochemical reduction of CO2 to CO in water at an overpotential of 340 mV with Faradaic efficiencies (FEs) of 93 %. These catalysts also show excellent stability without deactivation (<5 % productivity loss) within 72 hours of electrolysis. DFT calculation results further confirm the chelation effect in stabilizing molecule/NP interface and tailoring catalytic activity. This general approach is thus anticipated to be complementary to current NP catalyst design approaches.