Composition- and Condition-Dependent Kinetics of Homogeneous Ester Hydrogenation by a Mn-Based Catalyst

Area of Science:

• Computational chemistry
• Chemical kinetics
• Catalysis

Background:

• Homogeneous catalyst performance is dictated by reaction medium and conditions.
• Current density functional theory (DFT) models often simplify the reaction medium to an ideal solution, neglecting nonideal effects.

Purpose of the Study:

• To investigate the influence of reaction conditions and nonideal solution effects on the mechanism and kinetics of ester hydrogenation.
• To analyze the dynamic evolution of the reaction medium during catalysis.

Main Methods:

• Density functional theory (DFT) calculations.
• COSMO-RS solvent modeling.
• Microkinetic modeling.
• Operando computational modeling.

Main Results:

• Nonideal solvent effects and dynamic reaction media representations introduce nonlinearities into kinetic models.
• Computed energetics of elementary steps and kinetic profiles show strong condition dependencies.
• Experimentally observable kinetics like apparent activation energy are only slightly affected.

Conclusions:

• Accurate modeling of the reaction medium is essential for understanding homogeneous catalysis.
• Nonideal solution effects significantly alter computed energetics and kinetics, necessitating advanced modeling approaches.