Effective assessment of catalytic performance is the foundation for the rational design and development of new catalysts with superior performance. The ubiquitous screening/optimization studies use reaction yields as the sole performance metric in an approach that often neglects the complexity of the catalytic system and intrinsic reactivities of the catalysts. Using an example of hydrogenation catalysis, we examine the transient behavior of catalysts that are often encountered in activation, deactivation and catalytic turnover processes. Each of these processes and the reaction environment in which they take place are gradually shown to determine the real-time catalyst speciation and the resulting kinetics of the overall catalytic reaction. As a result, the catalyst performance becomes a complex and time-dependent metric defined by multiple descriptors apart from the reaction yield. This behaviour is not limited to hydrogenation catalysis and affects various catalytic transformations. In this feature article, we discuss these catalytically relevant descriptors in an attempt to arrive at a comprehensive depiction of catalytic performance.

Homogeneously catalyzed reactions often make use of additives and promotors that affect reactivity patterns and improve catalytic performance. While the role of reaction promotors is often discussed in view of their chemical reactivity, we demonstrate that they can be involved in catalysis indirectly. In particular, we demonstrate that promotors can adjust the thermodynamics of key transformations in homogeneous hydrogenation catalysis and enable reactions that would be unfavorable otherwise. We identified this phenomenon in a set of well-established and new Mn pincer catalysts that suffer from persistent product inhibition in ester hydrogenation. Although alkoxide base additives do not directly participate in inhibitory transformations, they can affect the equilibrium constants of these processes. Experimentally, we confirm that by varying the base promotor concentration one can control catalyst speciation and inflict substantial changes to the standard free energies of the key steps in the catalytic cycle. Despite the fact that the latter are universally assumed to be constant, we demonstrate that reaction thermodynamics and catalyst state are subject to external control. These results suggest that reaction promotors can be viewed as an integral component of the reaction medium, on its own capable of improving the catalytic performance and reshaping the seemingly rigid thermodynamic landscape of the catalytic transformation.

Any catalyst should be efficient and stable to be implemented in practice. This requirement is particularly valid for manganese hydrogenation catalysts. While representing a more sustainable alternative to conventional noble metal-based systems, manganese hydrogenation catalysts are prone to degrade under catalytic conditions once operation temperatures are high. Herein, we report a highly efficient Mn(I)-CNP pre-catalyst which gives rise to the excellent productivity (TOF° up to 41 000 h⁻¹) and stability (TON up to 200 000) in hydrogenation catalysis. This system enables near-quantitative hydrogenation of ketones, imines, aldehydes and formate esters at the catalyst loadings as low as 5–200 p.p.m. Our analysis points to the crucial role of the catalyst activation step for the catalytic performance and stability of the system. While conventional activation employing alkoxide bases can ultimately provide catalytically competent species under hydrogen atmosphere, activation of Mn(I) pre-catalyst with hydride donor promoters, e.g. KHBEt₃, dramatically improves catalytic performance of the system and eliminates induction times associated with slow catalyst activation.

Homogeneous hydrogenation catalysts based on metal complexes provide a diverse and highly tunable tool for the fine chemical industry. To fully unleash their potential, fast and effective methods for the evaluation of catalytic properties are needed. In turn, this requires changes in the experimental approaches to test and evaluate the performance of the catalytic processes. Design of experiment combined with statistical analysis can enable time- and resource-efficient experimentation. In this work, we employ a set of different statistical models to obtain the detailed kinetic description of a highly active homogeneous Mn (I) ketone hydrogenation catalyst as a representative model system. The reaction kinetics were analyzed using a full second order polynomial regression model, two models with eliminated parameters and finally a model which implements “chemical logic”. The coefficients obtained are compared with the corresponding high-quality kinetic parameters acquired using conventional kinetic experiments. We demonstrate that various kinetic effects can be well captured using different statistical models, providing important insights into the reaction kinetics and mechanism of a complex catalytic reaction.