ORGN 625 |
| The catalytic activation of the C-X bond is of major importance for synthetic chemistry. We show how the kinetics of this (and other processes) can be understood and predicted using an extended variant of our Activation Strain model. In this model, the (relative) energy ΔEtot along the reaction coordinate is decomposed into the strain of the reactants ΔEstrain and their mutual interaction energy ΔEint, see illustration (black: Pd + methane C-H; blue: Pd + ethane C-C). The energy of the transition state (i.e., the activation energy) as well as the position of the transition state (TS) along the reaction coordinate (e.g., early versus late TS) can now be understood in terms of the interplay between ΔEstrain and ΔEint, which are directly related to C-X bond strengths and the catalyst's electronic structure. This insight makes it possible to fine-tune the activity and selectivity of the catalyst complex in a rational manner.
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Physical Organic Chemistry: Calculations, Mechanisms, Photochemistry, and High-Energy Species
8:00 AM-12:00 PM, Thursday, 30 March 2006 Georgia World Congress Center -- C303, Oral
Division of Organic Chemistry |
