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The Elusive Silyliumylidene [ClSi:]+ and Silathionium [ClSi[DOUBLE BOND]S]+ Cations Stabilized by Bis(Iminophosphorane) Chelate Ligand


  • Financial support from the Deutsche Forschungsgemeinschaft (DR-17/2) is gratefully acknowledged.


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Donor–acceptor trumps: The chlorosilyliumylidene salt 2 with a three-coordinate silicon(II) atom is accessible through ligand exchange between NHC[BOND]SiCl2 and the electron-rich bis(ylide) ligand 1. The cation in 2 represents a donor-stabilized form of the elusive [ClSi:] cation and could be fully characterized, including X-ray diffraction analysis. Oxidation of 2 with elemental sulfur furnished 3 as the sole product.