“…Expansion to tertiary (3°) silanes has been a recent focus due to the relevance in industrial hydrosilylation, and particularly important advances have been made using alkoxy-substituted silanes to form the linear hydrosilylation products with exceptional regioselectivity. ,,,,,,,,,,, Despite these advances, most reports focus on 1 and 2° aryl silanes, emphasizing the need to develop catalysts that enable the hydrosilylation of 3° silanes, especially chloro- and alkoxy-substituted silanes (Figure b). Notably, only a handful of base-metal catalysts have been developed to react with chlorosilanes, and all of them either give poor selectivity or have limited scopes. ,,− Indeed, investigation and expansion of the silane scope are often neglected in hydrosilylation reactions, despite the fact that changes in both the silane’s electronic − and steric ,− characteristics impact reactivity and properties of hydrosilylation products.…”