School of Chemistry Colloquium: Professor Evgeny Pidko Death and Life of Homogeneous Carbonyl Reduction Catalysts: Navigating the Maze of Deactivation Chemistry for Sustained Performance

Catalytic reduction of carbonyl moieties in ketones and esters is fundamental to the production of high-value fine chemicals. Although traditional precious metal-based catalysts remain prevalent, first-row transition metals are emerging as compelling alternatives, thanks to their sustainability, economic advantages, and lower toxicity.[1] However, their practical implementation is often hampered by the fast catalyst deactivation under the reaction conditions.

This talk will highlight the crucial need for molecular-level understanding of both the catalytic and deactivation chemistry for catalyst design and optimization, with specific examples from our recent work on Mn-catalyzed carbonyl reduction.[2, 3, 4]

The efficiency of any given catalytic process is a complex function defined by the intrinsic chemistry of the catalyst and its dynamic interaction with the reactive environment under given reaction conditions.[5] The rate and selectivity of pre-catalyst activation, the compositional effects imposed by the reaction environment, and deactivation side-paths all play a role in determining the apparent kinetics and the outcomes of catalytic hydrogenations. In this lecture, I will discuss how a multifaced approach, integrating operando spectroscopy, kinetic studies, and computations, enables us to navigate the complex catalysis space, thereby improving both the activity and durability of 3d metal-based catalyst systems.

[1] G.A. Filonenko, R. van Putten, E.J.M. Hensen, E.A. Pidko, Chem. Soc. Rev. 2018, 47, 1459. [2] R. van Putten, E.A. Uslamin, M. Garbe, C. Liu, A. Gonzalez-de-Castro, M. Lutz, K. Junge, E.J.M. Hensen, M. Beller, L. Lefort, E.A. Pidko, Angew. Chem. Int. Ed. 2017, 129, 7639; W. Yang, I. Yu. Chernyshov, R. K. A. van Schendel, M. Weber, C. Müller, G. Filonenko, E. Pidko, Nat. Commun. 2021, 12, 12. [3] C. Liu, R. van Putten, P.O. Kulayev, G.A. Filonenko, E.A. Pidko, J. Catal. 2018, 363, 136; W. Yang, T. Kalavalapalli, A. Krieger, T.A. Khvorost, I. Yu. Chernyshov, M. Weber, E.A. Uslamin, E.A. Pidko, G. Filonenko, J. Am. Chem. Soc. 2022, 144, 8129. [4] A. Hashemi, S. Bougueroua, M.P. Gaigeot, E.A. Pidko, J. Chem. Theory Comput. 2022, 18, 7470; A. Hashemi, S. Bougueroua, M.-P. Gaigeot, E.A. Pidko, J. Chem. Inf. Model. 2023, 63, 6081. [5] W. Yang, G. Filonenko, E.A. Pidko, Chem. Commun. 2023, 59, 1757.