5 years ago

Silyl Chalconium Ions: Synthesis, Structure and Application in Hydrodefluorination Reactions

Silyl Chalconium Ions: Synthesis, Structure and Application in Hydrodefluorination Reactions
Natalie Kordts, Thorben Sieling, Sandra Künzler, Saskia Rathjen, Marc Schmidtmann, Henning Großekappenberg, Thomas Müller
The synthesis of two series of silylated chalconium borates, 9 and 10, which are based on the peri-naphthyl and peri-acenaphthyl framework, is reported (chalcogen (Ch): O, S, Se, Te). NMR investigations of the selenium- and tellurium-containing precursor silanes 3 d–f and 8 d, f revealed a significant through-space J-coupling between the chalcogen nuclei and the Me2SiH group. Experimental and computational results typify the synthesized cations 9 and 10 as chalconium ions. The imposed ring strain weakens the Si−Ch linkage compared to acyclic chalconium ions. This attenuation of the Si−Ch bond strength is more pronounced in the acenaphthene series. Surprisingly, the Si−O bonds in oxonium ions 9 a and 10 a are the weakest Si−Ch linkage in both series. The synthesized silyl chalconium borates are active in hydrodefluorination reactions of alkyl fluorides with silanes. A cooperative activation of the silane by the Lewis acidic (silicon) and by the Lewis basic side (chalcogen) is suggested. Oxygen breaks ranks: The structural, spectroscopic and computer–chemical characterization of two series of silylated chalconium ions (Ch=O, S, Se, Te) revealed significant differences between the second row element oxygen and its higher congeners.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201700995

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