Toward prediction of the precatalyst activation mechanism through the cross‐coupling reactions: Reduction of Pd( II ) to Pd(0) in precatalyst of the type Pd‐PEPPSI
Journal of Computational Chemistry Vol. 41, No. 26, 2296–2309
چکیده
Abstract Pd‐PEPPSI type complexes are widely used as precatalyst in a variety of organic reactions, including the Negishi, Kumada and Suzuki‐Miyaura cross‐coupling reactions. The aim of this research is to determine potential proposed reaction pathways 1, 2, or 2′ (See Schemes 1 and S1–S4 ) for Pd‐PEPPSI precatalyst activation in the presence of ethylene glycol as a solvent also in the gas phase at Cam‐B3LYP‐D3 method nominated among eight DFT methods examined. There is also investigation into the impact of promoter bases (NaOEt, NaOiPr, NaOtBu) on precatalyst activation of Pd‐PEPPSI. Eventually, the most favorable proposed reaction pathway and promoter base for reducing Pd(II) to Pd(0) are predicted computationally. Notably, our findings are consistent with the organ Pd‐PEPPSI type complexes that offer increased catalytic activity and provide basic information in the presence of solvents designing the monoligated Pd(0)‐solvent.