engleski

Radical-induced acidity enhancements

Relative C-H bond acidities of open and closed shell compounds containing activating ester, thioester, or keto groups have recently been calculated for simple model systems in order to elucidate the acid/base properties of radicals occurring as intermediates in enzyme-mediated transformations (2-hydroxyglutaryl-CoA dehydratase, methylmalonyl-CoA mutase). It was quite generally found that open shell systems are considerably more acidic than comparable closed shell analogs. The limits of accuracy of these studies have been tested using acetic acid and methanol in comparison to their respective neutral radicals. Acidities have been calculated using a selection of different electronic structure methods, continuum solvation methods, as well as combinations of continuum solvation/explicit solvation methods (continuum/cluster models).

radical; acidity; ab initio

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