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RESEARCH PRODUCT
Nickel-catalyzed carboxylation of aryl zinc reagent with CO2: A theoretical and experimental study
Mei-yan WangRoberts I. EglitisJing WangRan JiaRan JiaJian WangHong-xing ZhangGuoyin Yinsubject
Reaction mechanismProcess Chemistry and TechnologyArylTricyclohexylphosphine02 engineering and technology010402 general chemistry021001 nanoscience & nanotechnology01 natural sciencesMedicinal chemistry0104 chemical sciencesCatalysischemistry.chemical_compoundchemistryFerroceneCarboxylationReagentYield (chemistry)Chemical Engineering (miscellaneous)0210 nano-technologyWaste Management and Disposaldescription
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 ascribed the shortage of the reaction yield to the weak CO2 capture ability of the (dppf)Ni complex. Two additional ligands 1,2-bis(diphenylphosphino)ethane (dppe) and 1,4-bis(diphenylphosphino)butane (dppb) were also taken into account to verify the ligand effect in our reactions.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2019-01-01 | Journal of CO2 Utilization |