A Generalized Kinetic Model for Compartmentalization of Organometallic Catalysis

Compartmentalization is an attractive approach to enhance catalytic activity by retaining reactive intermediates and mitigating deactivating pathways. Such a concept has been well explored in biochemical and more recently, organometallic catalysis to ensure high reaction turnovers with minimal side reactions. However, a scarcity of theoretical framework towards confined organometallic chemistry impedes a broader utility for the implementation of compartmentalization. Herein, we report a general kinetic model and offer design guidance for a compartmentalized organometallic catalytic cycle. In comparison to a non-compartmentalized catalysis, compartmentalization is quantitatively shown to prevent the unwanted intermediate deactivation, boost the corresponding reaction efficiency (𝛾), and subsequently increase catalytic turnover frequency (𝑇𝑂𝐹). The key parameter in the model is the volumetric diffusive conductance (𝐹 ) that describes catalysts’ diffusion propensity across a compartment’s boundary. Optimal values of 𝐹 for a specific organometallic chemistry are needed to achieve maximal values of 𝛾 and 𝑇𝑂𝐹. Our model suggests a tailored compartment design, including the use of nanomaterials, is needed to suit a specific organometallic catalysis. This work provides justification and design principles for further exploration into compartmentalizing organometallics to enhance catalytic performance.