Outer‐Sphere Ionic Hydrosilylation Catalysis

Breaking ties: Recent reports on iridium and ruthenium homogeneous hydrosilylation catalysis point to a heterolytic activation of SiH bonds promoted by the oxophilicity of the silicon atom and the Lewis acidity of the metal center. This unusual type of mechanism opens the door to a more widespread use of catalysts that operate by an ionic or concerted outer‐sphere mechanism in organic synthesis.