Abstract
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.
Highlights
Increasing demand in chemicals and fuels puts forward new challenges for chemical industry and chemistry in general
*x1 þ b2x2 þ b3x3þ b4x4 þ x5 þ b5x6 with x2 being pressure in bar, x3 being the natural logarithm of the catalyst concentration, x4 being the natural logarithm of base concentration, x5 being the natural logarithm of the substrate concentration at the end of the reaction and x6 being the reaction time in seconds and the corresponding coefficient β5 being the rate constant for catalyst activation
The results presented highlight the critical role of the secondary effects such as the reaction temperature and the presence and concentration of base activator/promotor on the performance of the homogeneous carbonyl hydrogenation catalysts
Summary
Increasing demand in chemicals and fuels puts forward new challenges for chemical industry and chemistry in general. A number of highly active homogeneous carbonyl hydrogenation catalysts based on defined transition metal complexes, e. G. ruthenium, iridium, and rhodium, were developed Many of these catalysts enable highly selective homogeneous hydrogenation under mild conditions.[4b,5] the possibility to use cheaper earthabundant 3d metal complexes as an alternative to their noble metal based counterparts has drawn considerable attention recently.[6,7] Figure 1 presents selected representative examples of such highly-active catalysts. The availability of kinetic data and its accurate modelling would provide a comprehensive insight in the behavior and mechanisms of catalytic reactions and facilitate further development and optimization of highly efficient hydrogenation catalyst systems.[16]. We demonstrate that this approach can indicate hidden parameters which are not observed during the conventional kinetic experiments
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