Silatranylnitrilium Hexachloridoantimonate, its Brønsted Base‐Assisted CC‐Bond Formation and Transformation to an Unprecedented Carbene‐Type SbCl ₅ Complex

Silylium ions, three‐coordinated as well as donor‐stabilized, have attracted the interest of chemists for many years, have paved its way into practical application as catalysts for organic reactions, and have contributed to the understanding of fundamental chemistry problems. Since the first carbenes have been isolated and characterized, they had and still have an ongoing enormous impact on organic as well as on inorganic and organometallic chemistry. Herein, the synthesis and complete characterization of silatranyl cations as their acetonitrile‐ respectively propionitrile‐coordinated hexachlorido antimonates is reported. Upon interaction of the former with 4‐dimethylaminopyridine (DMAP) conversion to an unprecedented carbene–type complex of antimony pentachloride occurred, nicely combining silylium and carbene chemistry.