Combined Theoretical and Experimental Investigation of Lewis Acid-Carbonyl Interactions for Metathesis

The coordination of a carbonyl to a Lewis acid represents the first step in a wide range of catalytic transformations. In many reactions it is necessary for the Lewis acid to discriminate between starting material and product, and as a result, how these structures behave in solution must be characterized. Herein, we report the application of computational modeling to calculate properties of the solution interactions of acetone and benzaldehyde with FeCl₃. Using these chemical models, we can predict spectral features in the carbonyl region of infrared (IR) spectroscopy. These simulated spectra are then directly compared to experimental spectra generated via titration-IR. We observe good agreement between theory and experiment, in that, between 0 and 1 equiv carbonyl with respect to FeCl₃, a pairwise interaction dominates the spectra. When >1 equiv carbonyl is present, our theoretical model predicts two possible structures composed of 4:1 carbonyl to FeCl₃, for acetone as well as benzaldehyde. When these predicted spectra are compared with titration-IR data, both structures contribute to the observed solution interactions. These findings suggest that the resting state of FeCl₃-catalyzed carbonyl-based reactions employing simple substrates starts as a Lewis pair, but this structure is gradually consumed and becomes a highly ligated, catalytically less active Fe-centered complex as the reaction proceeds. An analytical model is proposed to quantify catalyst inhibition due to equilibrium between 1:1 and 4:1 carbonyl:Fe complexes.