DFT Study of the Ethylene Hydroformylation Catalytic Cycle Employing a HRh(PH3)2(CO) Model Catalyst

June 25, 2001

Journal Article

DFT Study of the Ethylene Hydroformylation Catalytic Cycle Employing a HRh(PH3)2(CO) Model Catalyst

Abstract

The potential energy hypersurface for ethylene hydroformylation catalyzed by HRh(PH3)2- (CO) was mapped out at the CCSD(T)//B3LYP and B3LYP//B3LYP levels of theory using effective core potentials. Combining the results obtained for each elementary step there are a number of possible pathways for the hydroformylation catalytic cycle, originating from the trans (2a) and cis (2b) isomers of the active catalyst. At both levels of theory employed, a preference was predicted for the pathways originating from the trans isomer of the active catalyst, 2a. The alternative pathways originating from the cis isomer, 2b, were discounted because of the large activation barriers predicted for the two migratory insertion reactions, arising from unfavorable interactions between the equatorial phosphine ligands and the migrating axial ligand.

Revised: January 23, 2012 | Published: June 25, 2001

Citation

Decker S.A., and T.R. Cundari. 2001. DFT Study of the Ethylene Hydroformylation Catalytic Cycle Employing a HRh(PH3)2(CO) Model Catalyst. Organometallics 20, no. 13:2827-2841.