Reactions between a sodium amide Na[N(SiMe3)R1] (R1 = SiMe3, SiMe2Ph or But) and a cyanoalkane RCN (R = Ad or Bu(t))

Reactions between sodium amides NaN(SiMe3)R1] R1 = SiMe3 (1), SiMe2Ph (2) or But (3)] and cyanoalkanes RCN (R = Ad or But) were investigated. In each case the nitrile adduct Na{mu-N(SiMe3)2}(NCR)]2 R = Ad (1a) or But (1b)], trans-Na{mu-N(SiMe3)(SiMe2Ph)}(NCR)]2 R = Ad (2a) or But (2b)], (Na{mu-N(SiMe3)But})3(NCAd)3] (3a) or (Na{mu-N(SiMe3)But})3(NCBut)n] n = 3 (3b) or 2 (3c)] was isolated. The reaction of complexes 3a or 3b with benzene afforded the ketimido complex Na{mu-N=C(Ad)(Ph)}]6.2C6H6 (4a) or Na{mu-N=C(But)(Ph)}]6 (4b); the former was also prepared in more conventional fashion from NaPh and AdCN. The synthesis and structure of an analogue of complex 1a, Li{mu-N(SiMe3)2}(NCAd)]2 (5a), is also presented. The compounds 1a, 1b, 2a, 2b, 3, 3b, 4a, 4b and 5a were characterised by X-ray diffraction.