An explicit account of solvation is essential for modeling Suzuki-Miyaura coupling in protic solventsElectronic supplementary information (ESI) available. See DOI: 10.1039/c5dt03126e

• Main Authors: Zeifman, Alexey A, Novikov, Fedor N, Stroylov, Victor S, Stroganov, Oleg V, Svitanko, Igor V, Chilov, Ghermes G
• Format: Journal Article
• Language: English
• Published: 06.10.2015
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c5dt03126e

We compared explicit and implicit solvation approaches in modeling the free energy profile of the final step of Suzuki-Miyaura coupling. Both approaches produced similar Δ G ≠ in all the studied solvents (benzene, toluene, DMF, ethanol, and water). Solvation free energies of individual reaction components reasonably correlated for explicit and implicit models in aprotic solvents (RMSE = 30-50 kJ mol −1 , R 2 > 0.71). However for ethanol and water the correlation was poor. We attributed this difference to the formation of the Pd H-O hydrogen bond with Pd(PPh 3 ) 2 which was surprisingly observed in explicit modeling. Further QM calculations of the Pd(PPh 3 ) 2 -H 2 O system confirmed the direction (Pd H) and stability of this bonding. Therefore we stress the need for considering explicit solvation for modeling Pd-catalyzed reactions in protic solvents. We compared explicit and implicit solvation approaches in modeling the free energy profile of the final step of Suzuki-Miyaura coupling.