The discovery of homogeneous catalysts that preferentially form one product over another during regio- or enantioselective chemical reactions has traditionally been the province of experimental chemists. Computation has also impacted homogeneous catalysis, although most contributions are limited to the elucidation of reaction mechanisms and their associated free energy profiles. Given growing interest in designing new catalysts <i>in silico</i>, new tools are needed capable of accelerating the discovery process. With this in mind, our group recently transferred the concept of volcano plots, widely used tools in hetereogeneous and electrocatalysis, to the study of homogeneous systems. Subsequent adaptations allowed direct prediction of both the stability of intermediates and activation barrier heights for an industrially important process, the hydroformylation of olefins. Here, we show a new tool built on molecular volcano plots can be used to quickly predict both the activity of molecular catalysts as well as to estimate their intrinsic ability to preferentially form one of two regioisomers (see reaction scheme in the figure). Validation of the method over an independent test set of catalysts shows promising accuracy for the method. With this information in hand, we hunt for catalysts that preferentially form tertiary aldehydes, in violation of Keulemans’ law.

Identifying highly active and regioselective homogeneous catalysts from molecular volcano plots

256th National Meeting (2018)

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