The use of templates to preorganize two reactants in a supramolecular complex to reduce the entropy of activation for the subsequent reaction is well established. We have investigated this process by DFT calculations using several functionals for a number of published pseudo-intramolecular Diels-Alder reactions (self-replicating systems) and discovered unanticipated cooperative effects of significant magnitude. We will highlight the consequences for kinetic modelling and demonstrate the need for an accurate description of dispersion interactions in these medium-sized systems. 

Cooperative effects caused by dispersion in supramolecular reaction systems

244th National Meeting (2012)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.