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Experimental study demonstrates efficient sequential alkene disilylation via dual cobalt-nickel catalysis, highlighting a record turnover number of 24,000 driven by trace nickel species.
Comprehensive Summary gem ‐Bis(silanes) have attracted significant attention due to their unique reactivity and functionality. Herein, we report a highly efficient Co/Ni‐catalyzed dehydrogenative silylation/hydrosilylation reaction of alkenes for the construction of gem ‐bis(silanes). The unanticipated nickel impurities efficiently drive the key hydrosilylation step, enabling a high turnover number ( TON ) of up to 24,000. This reactivity represents the highest TON achieved for nickel‐catalyzed hydrosilylation of alkenes. Mechanistic studies have revealed that the silicon‐based directing effect plays a crucial role in governing both the reactivity and selectivity of this process. Furthermore, by controlling the nature of the nickel–hydride species, the key hydrosilylation step can be switched between geminal and vicinal pathways.
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Li et al. (2026) studied this question.
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