Important stoichiometric transformations like Wittig and Appel reactions have been implemented in a catalytic fashion in the past decade. The phosphine oxide generated in situ can be reintroduced as phosphine into the catalytic cycle using mild and selective silane reagents (redox-driven catalysis). While the field of experimental investigation has been fully expanding in the past decade, theoretical studies are still sparse. In this present work, density functional theory (DFT) has been used to characterize the free energy surfaces of the reduction of 1-phenyl phospholane 1-oxide with four different silanes. Found stationary points have been studied in-depth to highlight mechanistic peculiarities, like the effect of substituents at the silicon center and the parallel and competitive reactivity between the precursor silanes and their semioxidized byproducts. Calculated thermodynamic parameters in combination with “real” values for concentrations have been used in the formulation of rate equations for simple bimolecular and monomolecular steps of the mechanism. The deterministic integration concentrations versus time of such rate equations led to a realistic description of the systems under study and paved the way to strategic and rational design of new silanes with increased reactivity.