Do B3LYP and CCSDT predict different hydrosilylation mechanisms? Influences of theoretical methods and basis sets on relative energies in ruthenium-silylene-catalyzed ethylene hydrosilylation.
A series of density functional theory (DFT) and wave function theory (WFT) methods were used in conjunction with a series of basis sets to investigate the influence of the computational methodology on the relative energies of key intermediates and transition states in potential reaction pathways in ruthenium-silylene-catalyzed hydrosilylation reactions. A variety of DFT methods in a modest basis set and B3LYP calculations in a variety of basis sets calculated the key transition in the Glaser-Tilley (GT) pathway to be energetically favored. In contrast, with the smaller basis sets, the CCSD(T) method calculated the Chalk-Harrod (CH) pathway to be favored; however, CCSD(T) results extrapolated to larger basis sets favored the GT pathway.
Beddie
Chad
C
Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, TX 77842-3012, USA.
Hall
Michael B
MB