N‐Methyl‐Benzothiazolium Salts as Carbon Lewis Acids for Si−H σ‐Bond Activation and Catalytic (De)hydrosilylation

N−Me‐Benzothiazolium salts are introduced as a new family of Lewis acids able to activate Si−H σ bonds. These carbon‐centred Lewis acids were demonstrated to have comparable Lewis acidity towards hydride as found for the triarylboranes widely used in Si−H σ‐bond activation. However, they display low Lewis acidity towards hard Lewis bases such as Et3PO and H2O in contrast to triarylboranes. The N−Me‐benzothiazolium salts are effective catalysts for a range of hydrosilylation and dehydrosilylation reactions. Judicious selection of the C2 aryl substituent in these cations enables tuning of the steric and electronic environment around the electrophilic centre to generate more active catalysts. Finally, related benzoxazolium and benzimidazolium salts were found also to be active for Si−H bond activation and as catalysts for the hydrosilylation of imines. Soft skills: N‐methyl‐benzothiazolium cations are introduced as effective catalysts for Si−H σ‐bond activation, with particular focus on (de)hydrosilylation reactions. Substitution of the C2 aryl group or replacement of the sulphur with other heteroatoms has been investigated, both computationally and experimentally.