cs501828e_si_001.pdf (3.87 MB)
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
journal contribution
posted on 2015-03-06, 00:00 authored by Thomas
J. L. Mustard, Paul A. Wender, Paul Ha-Yeon CheongThe
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.