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

The 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) S(N)2-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.

Automated summary

The study elucidated two possible pathways for Si-Cl bond activation in Pd-catalyzed coupling reaction, providing insights for rational catalyst design.