Kinetic Influence of Electrophile‐Alkene Exchange of Nickel‐Alkene Complexes in Oxidative Addition ^†

Comprehensive Summary The oxidative addition of electrophiles to transition metals is a fundamental step in transition‐metal‐mediated cross‐coupling reactions. Although the mechanism of transition‐metal‐enabled C–X bond cleavage has garnered significant attention due to its impact on reaction selectivity and reactivity, the preceding association step between the electrophile and metal has long been underappreciated, particularly with regard to its kinetic effects. Here, we report and validate an associative electrophile‐alkene exchange (E A A) strategy using nickel(0)‐alkene complexes. This approach shifts the rate‐determining step from C–X bond cleavage to electrophile‐alkene exchange. By doing so, it enables selective recognition of C(sp 2 )‐electrophiles based on their coordination kinetics rather than bond dissociation energies, thereby facilitating the selective oxidative addition of C–F bonds over more reactive C–Cl, C–Br, and C–I bonds. Mechanistic studies reveal that the selective coordination of C(sp 2 )‐electrophiles depends on the coordination propensity of the pre‐coordinated alkene and the supporting ligand on the nickel(0) complex. This strategy not only complements the traditional reactivity trends of C–X bonds in oxidative addition but also provides a foundation for the rational design of catalysts and the development of more efficient chemical processes.