The efficient synthesis of hydrosilanes by catalytic hydrogenolysis of chlorosilanes is described, using an iridium (III) pincer catalyst. A careful selection of a nitrogen base (incl. sterically hindered guanidines and phosphazenes) can unlock the preparation of Me3SiH, Et3SiH and Me2SiHCl in high yield (up to 98%), directly from their corresponding chlorosilanes.

Hydrosilanes are convenient reductants for a large variety of organic substrates, but they are produced via energy-intensive processes. These limitations call for the development of general catalytic processes able to transform Si-O into Si-H bonds. We report here the catalytic hydrogenolysis of R3SiOTf (R = Me, Et, Ph) species in the presence of a base (e.g. NEt3), by the hydride complexes [( tBu-POCOP)IrH(X)] (X = H, OTf; ( tBu POCOP = [(1,3-C6H3)(OPtBu)2]). Syntheses and crystal structures of new iridium(I) and iridium(III) complexes are presented as well as their role in the R3SiOTf to R3SiH transformation. The mechanisms of these reactions have been examined by DFT studies, revealing that the rate-determining step is the base-assisted splitting of H2

The metal‐free catalytic hydrogenolysis of silyl triflates and halides (I, Br) to hydrosilanes is unlocked by using arylborane Lewis acids as catalysts. In the presence of a nitrogen base, the catalyst acts as a Frustrated Lewis Pair (FLP) able to split H2 and generate a boron hydride intermediate capable of reducing (pseudo)halosilanes. This metal‐free organocatalytic system is competitive with metal‐based catalysts and enables the formation of a variety of hydrosilanes at room temperature in high yields (>85 %) under a low pressure of H2 (≤10 bar).