Computational Organometallic Catalysis: Where We Are, Where We Are Going

Abstract

Dedicated to Professor Joan Bertran, who opened the doors to the quantum world for me, on the occasion of his 90th birthday This essay gives my personal perspective of the current stage of computational methods applied to modeling organometallic catalysis, as well as the new directions the field is taking. The first part of the essay deals with what I consider the state-ofthe-art to build up energy profiles, regarding both chemical and computational models. With a proper choice of the chemical model and computational methods, quantum mechanical calculations are nowadays able to provide accurate energy profiles of organometallic reactions in solution involving closed-shell species. However, in most cases they are still used to "predict the past", providing after-the-fact explanations and missing out the full potential of contemporary simulation techniques. Simulations are mature enough to be incorporated at the design stage and to guide the experimental exploration. The new directions the field is taking, incorporating automated exploration methods and combined with extensive data analysis and machine learning algorithms, approach the holy grail of catalyst discovering.

C–H Insertion in Dirhodium Tetracarboxylate-Catalyzed Reactions despite Dynamical Tendencies toward Fragmentation: Implications for Reaction Efficiency and Catalyst Design

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Computational Study for CO2-to-CO Conversion over Proton Reduction Using [Re[bpyMe(Im-R)](CO)3Cl]+ (R = Me, Me2, and Me4) Electrocatalysts and Comparison with Manganese Analogues

“…The detailed calculated TOFs and “degree of TOF control” (X TOF ) can be found in the Supporting Information (Tables S6–S9). We note that microkinetic modeling is another approach that is often used in homogeneous catalysis. − Still, the ESM allows us to compare the experimental selectivity for CO formation over H + reduction by relating the computed Gibbs free energies and turnover frequency (TOF). − …”

Computational Studies on the Mechanisms for Deaminative Amide Hydrogenation by Homogeneous Bifunctional Catalysts

“…DFT calculations and mixed experimental-theoretical studies have made a major contribution towards a deeper understanding of the mechanisms underlying the catalytic reactions [48,49]. Deaminative hydrogenation of amides has not been an exception.…”