Computational Insights into the Effect of Ligands and Transition-Metal Centers on the Mechanism and Regioselectivity of Hydrosilylation of Alkenes

Development of sustainable synthetic methods for the hydrosilylation of alkenes, catalyzed by 3d transition metals, offers a promising alternative to traditional noble metal catalysts. This study presents a computational mechanistic investigation into the hydrosilylation of alkenes, focusing on the role of ligands and metal centers in modulating the reaction's mechanism and regioselectivity. The ligand's electronic and steric properties were found to modulate the regioselectivity for cobalt catalysts, with phosphine ligand (xantphos) promoting higher linear selectivity compared to nitrogen-based ligand (^mesPDI). The energy decomposition analysis reveals that the xantphos ligand favors linear products due to stronger electrostatic and orbital interactions despite increased steric repulsion. The metal center also plays a crucial role, with cobalt catalysts favoring the modified Chalk-Harrod mechanism for branched product formation in the presence of <i>PNN</i> ligand (^<i>i</i>PrP^CNN^Me), due to lower activation barriers in alkene insertion. Beneficial electrostatic and orbital interactions predominate, rendering the alkene insertion transition state for cobalt more favorable compared to that for iron. This work provides a comprehensive understanding of how ligand and metal center effects can be harnessed to control regioselectivity in hydrosilylation reactions.