Synthesis of N-substituted derivatives of the hypho-(amine)(amino)B8H11 system

The chemistry of the hypho-(amine)(amino)B8H11 system is developed by the synthesis of several derivatives by three routes. [(Et2HN)B8H11NEt2] (4), characterised by single-crystal X-ray work, is prepared from the reaction between B9H13(SMe2) and Et2NH. Methylation of [(EtH2N)B8H11NHEt] (1) using NaH and MeI gives, successively, [(EtMeHN)B8H11NHEt] (5), [(EtMe2N)B8H11NHEt] (6) and [(EtMe2N)B8H11NMeEt] (7). Alternatively, a displacement reaction with NHEt2 on (1) or on [(MeH2N)B8H11NHMe] (2) yields [(Et2HN)B8H11NHEt] (8) or [(Et2HN)B8H11NHMe] (9), and a displacement on (1) with pyridine yields [(C5H5N)B8H11NHEt] (10). Phosphine-containing derivatives [(Ph3P)B8H11NHEt] (11) and [(PhMe2P)B8H11NHEt] (12) can be isolated from interaction of (1) with PPh3, [RhCl(PPh3)3] or [PtCl2(PMe2Ph)2].