title: Catalytic Efficiency Is a Function of How Rhodium(I) (5 + 2) Catalysts Accommodate a Conserved Substrate Transition State Geometry: Induced Fit Model for Explaining Transition Metal Catalysis.
abstract: The origins of differential catalytic reactivities of four Rh(I) catalysts and their derivatives in the (5 + 2) cycloaddition reaction were elucidated using density functional theory. Computed free energy spans are in excellent agreement with known experimental rates. For every catalyst, the substrate geometries in the transition state remained constant (<0.1 Å RMSD for atoms involved in bond-making and -breaking processes). Catalytic efficiency is shown to be a function of how well the catalyst accommodates the substrate transition state geometry and electronics. This shows that the induced fit model for explaining biological catalysis may be relevant to transition metal catalysis. This could serve as a general model for understanding the origins of efficiencies of catalytic reactions.
authors.affiliation: Department of Chemistry, Oregon State University, 153 Gilbert Hall, Corvallis, Oregon 97331-4003, United States.
authors.forename: Thomas J L
authors.initials: TJ
authors.lastname: Mustard
authors.affiliation: Departments of Chemistry and Chemical and Systems Biology, Stanford University, Stanford, California 94305-5080, United States.
authors.forename: Paul A
authors.initials: PA
authors.lastname: Wender
authors.affiliation: Department of Chemistry, Oregon State University, 153 Gilbert Hall, Corvallis, Oregon 97331-4003, United States.
authors.forename: Paul Ha-Yeon
authors.initials: PH
authors.lastname: Cheong
keywords: DFT; NHC; catalysis; computations; ligands; organometallic; phosphine; rhodium; theory; transition metals