The current computational study with density functional theory (DFT) shows that the rate of chemical reactions can be influenced through non-covalent C–H/π interactions between substrates and the solvent. It is shown that intramolecular carbon–carbon interaction and CO₂ activation by a low valent silicon complex are both favourably affected by the explicit presence of the solvent toluene, due to C–H/π interactions between toluene and the silicon complex. Furthermore, ab initio molecular dynamics (AIMD) simulations demonstrate that even if the C–H/π interacting solvent molecule is displaced from the complex, another would quickly take its place, thus maintaining the interaction. Hence, the current work shows how non-covalent interactions between solvent and substrate can enhance the rate of the reaction and expands our understanding of the role and influence of the solvent in effecting important chemical transformations.