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

Zeinab Ahmadvand; Mehdi Bayat; Mohammad Ali Zolfigol

doi:10.1002/jcc.26393

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

J Comput Chem. 2020 Oct 5;41(26):2296-2309. doi: 10.1002/jcc.26393. Epub 2020 Aug 5.

Authors

Zeinab Ahmadvand¹, Mehdi Bayat¹, Mohammad Ali Zolfigol²

Affiliations

¹ Department of Inorganic Chemistry, Faculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran.
² Department of Organic Chemistry, Faculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran.

PMID: 32757323
DOI: 10.1002/jcc.26393

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, NaOⁱ Pr, NaO^t Bu) 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.

Keywords: DFT; Pd-PEPPSI; mechanism; palladium; precatalyst activation.

Publication types

Research Support, Non-U.S. Gov't