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On the basis of Kohn᎐Sham density functional DFT investigations on elementary organic and organometallic reactions, we show how a detailed understanding of the electronic structure of a reaction system can help recognize certain characteristics of the process, yielding valuable mechanistic concepts. The concept of the base as a selective catalyst in E2 eliminations, for example, leads to a straightforward explanation for the general preference for anti over syn stereochemistry in base-induced elimination reactions. Furthermore, electronic structure considerations provide the so-called E2᎐S 2 mechanistic spectrum, in terms of which one can interpret and N understand the competition between elimination and substitution reactions and the shift, on solvation, of the reactivity from E2 to S 2. In addition, mechanistic N concepts from organometallic and organic chemistry are linked as we argue that oxidative addition may be conceived, in some respect, as the organometallic analog of the frontside S 2 substitution. Finally, we introduce the ideas of N ''activation strain'' of and ''transition state interaction'' between the deformed reactants in the activated complex, which together determine the activation energy, ⌬ E U s ⌬ E U q ⌬ E U. They prove to be helpful conceptual tools for strain int understanding in detail how activation barriers and relative efficiencies of Ž competing reaction mechanisms arise and how they may be affected e.g., by. changing reactants or by solvation .

Understanding reactivity with Kohn-Sham molecular orbital theory: E2-SN2 mechanistic spectrum and other concepts