Chemoselective Recognition of Vinyl Organometalloids in Cobalt‐Catalyzed Hydrosilylation

Achieving selective functionalization of vinylsilanes in the presence of other terminal C═C bonds remains a significant challenge in organosilicon chemistry. Here, we report a cobalt catalyst supported by a bidentate aminophosphine ligand that enables highly chemoselective hydrosilylation of terminal vinylmetalloids under mild, solvent‐free conditions. The earth‐abundant system operates without external activators, as the hydrosilane substrate itself promotes catalyst activation. Remarkably, reactivity is restricted to terminal vinylmetalloid motifs, encompassing vinylsilanes, vinylgermanes, and vinylboronates, whereas allylsilanes, terminal alkenes, internal alkenes, and 1,1‐disubstituted derivatives remain unreactive. This unusual selectivity enables exclusive transformation of vinylmetalloid groups even in multifunctional substrates containing olefinic sites. Control of substrate stoichiometry further provides access to structurally diverse organosilicon products from multiple‐vinyl precursors with high efficiency.