Abstract
Ph~3~SnN(SiMe~3~)~2~ (1) was prepared in good yields by reaction of [{NaN(SiMe~3~)~2~}~2~·THF] (2) with Ph~3~SnF. Treatment of 1 with [H(OEt~2~)~2~][H~2~N{B(C~6~F~5~)~3~}~2~] (4) in dichloromethane afforded the stannylium cation [Ph~3~Sn(OEt~2~)][H~2~N{B(C~6~F~5~)~3~}~2~] (5), which was characterised by ^1^H, ^13^C{^1^H}, ^11^B, ^19^F and ^119^Sn NMR spectroscopy. The reaction of Sn(NMe~2~)~4~ with [Ph~2~MeNH][B(C~6~F~5~)~4~] (3) gave the amidotin(IV) compound [Sn(NMe~2~)~3~(HNMe~2~)~2~][B(C~6~F~5~)~4~] (6) which proved very stable towards ligand substitution and resisted treatment with Et~2~O, THF, TMEDA and pyrazine. Two new Brønsted acid salts [H(NMe~2~H)~2~][B(C~6~F~5~)~4~] (7) and [(C~4~H~4~N~2~)H·OEt~2~][H~2~N{B(C~6~F~5~)~3~}~2~] (8) were synthesised. The reaction of 7 with Sn(NMe~2~)~4~ in Et~2~O allowed the preparation of 6 in a much improved yield (83 %). The treatment of 7 with Me~3~SnN(SiMe~3~)~2~ in Et~2~O yielded [Me~3~Sn(HNMe~2~)~2~][B(C~6~F~5~)~4~] (9) nearly quantitatively. Compounds 1, 2, 6, 8 and 9 were characterised by single‐crystal X‐ray diffraction analyses; 6 is the first example of a structurally characterised amidotin(IV)cation.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)