Concentration‐Dependent Thermodynamics of the Inhibitory Paths in Homogeneous Mn(I) Hydrogenation Catalysis

Many catalytic reactions suffer from product inhibition, which especially hard to control in homogeneous hydrogenation due to the scaling relation between the inhibited and active states of the catalyst. We recently reported one such pathway in Mn(I) hydrogenation and demonstrated that addition of alkoxide bases could affect the thermodynamic favorability of this reaction and selectively suppress the product inhibition. Since external reaction promotors are formally not involved in reaction thermodynamics, we set to investigate the explicit molecular interactions behind these apparently environmental effects. Herein, we reveal that the thermodynamic landscape of the inhibitory process exhibits a non‐monotonic dependence on the base concentration. We related this phenomenon to the presence of two dominant mechanisms operating at different base concentrations. Specifically, the base additives can enhance the ionic strength and lower the free energy of the inhibited state at low promotor concentration. At high base concentrations we suggest the formation of highly labile alcohol‐alkoxide clusters which stabilize the free alcohol and make its addition to the catalyst unfavourable, thereby suppressing the inhibition. While relatively weak, such non‐covalent interactions between reactants and reaction environment can cause substantial perturbations to the free energy of catalytic process, ultimately deciding its fate.