Activation of Si-H and B-H bonds by Lewis acidic transition metals and p-block elements: same, but different.

In this we discuss the ability of transition metal complexes to activate and cleave the Si-H and B-H bonds of hydrosilanes and hydroboranes (tri- and tetra-coordinated) in an electrophilic manner, avoiding the need for the metal centre to undergo two-electron processes (oxidative addition/reductive elimination). A formal polarization of E-H bonds (E = Si, B) upon their coordination to the metal centre to form σ-EH complexes (with coordination modes η or η) favors this type of bond activation that can lead to reactivities involving the formation of transient silylium and borenium/boronium cations similar to those proposed in silylation and borylation processes catalysed by boron and aluminium Lewis acids. We compare the reactivity of transition metal complexes and boron/aluminium Lewis acids through a series of catalytic reactions in which pieces of evidence suggest mechanisms involving electrophilic reaction pathways.