Nickel-catalyzed carboxylation of aryl zinc reagent with CO2: A theoretical and experimental study

Abstract Two Ni-complexes with 1,1′-bis(diphenylphosphino)ferrocene (dppf) and tricyclohexylphosphine (PCy3) ligands were tested for the Ni-catalyzed cross-coupling of aryl zinc reagent with CO2 to form aryl carboxylic acid. Theoretical study with the aid of density functional theory (DFT) was carried out to understand the detailed reaction mechanism. The reasonable reaction pathway was deduced. The simulation results suggested that the free energy barrier of the rate-limiting step with (dppf)Ni is only 1.64 kcal mol−1 higher than the barrier with (PCy3)2Ni. However, our experiment provided an unexpectedly low yield by using (dppf)Ni complex as the catalyst. Further theoretical study ascrib…