Alkylderivatives of Stanna-closo-dodecaborate

The reactions of [SnB11H11]2− with organic halides like 1-chloro-3-iodopropane, allylbromide, propargylbromide and 2,6-bis-(bromomethyl)pyridine lead in a nucleophilic substitution at room temperature to the products [Bu3MeN][Cl(CH2)3SnB11H11] (4), [Bu3MeN][H2CCHCH2SnB11H11] (6), [Bu4N][HCCCH2SnB11H11] (7), and [Bu4N]2[2,6-(H11B11SnCH2)2(C5H3N)] (8). In water Na2[SnB11H11] reacts with 2-bromoethylamine hydrobromide at 50 °C and 3-bromopropylamine hydrobromide at 70 °C to the zwitterionic products [H11B11Sn(CH2)nNH3] (n=2, 3), which were characterized by X-ray crystal structure analysis. [H11B11Sn(CH2)2NH3] crystallizes with one equivalent of water under the formation of NHO hydrogen bonding. In the case of chloroiodomethane and diiodomethane the substitution reaction proceeds differently and the monosubstituted components were not detected. The disubstituted compound [Bu3MeN]2[H2C(SnB11H11)2] (5), whose structure could be confirmed by X-ray crystal structure analysis, is the only observed reaction product.