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Chlorine/Methyl Exchange Reactions in Silylated Aminostibanes: A New Route To Stibinostibonium Cations

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journal contribution
posted on 06.08.2012, 00:00 by Christian Hering, Mathias Lehmann, Axel Schulz, Alexander Villinger
The Lewis acid assisted triflate/methyl, azide/methyl, and chlorine/methyl exchange reactions between silicon and antimony have been studied in the reaction of R­(Me3Si)­N–SbCl2 (R = Ter) with AgOTf, AgN3, KOtBu, GaCl3, and Me3SiN3/GaCl3, resulting in the formation of different methylantimony compounds. Furthermore, R­(Me3Si)­N–SbCl2 (R = SiMe3) was reacted with GaCl3 at low temperatures to yield a hitherto unreported amino­(chloro)­stibenium cation, the proposed intermediate in methyl exchange reactions. Tetrachloridogallate salts bearing different stibinostibonium cations such as [(Me3Sb)­SbMe2]+ and [(Me3Sb)2SbMe]2+ along with the GaCl3 adduct of SbMe3 were isolated from such R­(Me3Si)­N–SbCl2/GaCl3 mixtures (R = SiMe3) at ambient temperatures, depending on the reaction parameters.

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