The controversy over how free the trivalent silicon cation is placed the emphasis on their spectroscopic and crystallographic characterisation. Those investigations contributed substantially to the understanding of the role of σ or π Lewis basic molecules in the chemistry of extremely potent Lewis acids, culminating in the discovery of innocent, that is non-coordinating, anions and an X-ray molecular structure. Synthetic uses of such reactive intermediates are however underrepresented yet a few recent contributions offer a glimpse of their true potential. This perspective provides a concise overview of known silylium ions, followed by examples of their uses as catalysts in C-F bond activation and C-C bond formation, namely challenging Diels-Alder reactions.
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