Theoretical Study on Si−Cl Bond Activation in Pd‐Catalyzed Cross‐Coupling of Chlorosilanes with Organoaluminum

Abstract

AbstractThe catalytic cross‐coupling of chlorosilanes has recently emerged as an efficient method for the synthesis of organic silicon compounds. Direct Si−Cl bond activation by transition metals is a key elementary reaction in these methods. This theoretical study aimed to elucidate the mechanism of activation of the strong Si−Cl bond in Pd‐catalyzed coupling reaction to gain insights for rational catalyst design. Our results suggest two plausible pathways for the bond activation: (i) trans‐oxidative addition and (ii) SN2‐type oxidative addition assisted by a Lewis acid. With an increase in Cl substituents of chlorosilanes, trans‐oxidative addition highly feasible due to their higher Lewis acidities, in which the facile formation of the Pd→Si interaction enables the smooth activation of the Si−Cl bond. The general mechanism of direct Si−Cl bond activation presented here may prove useful for the rational design of catalysis in the future.