Reactions between sodium amides Na[N(SiMe₃)R¹] [R¹ = SiMe₃ (1), SiMe₂Ph (2) or Bu^t (3)] and cyanoalkanes RCN (R = Ad or Bu^t) were investigated. In each case the nitrile adduct [Na{µ-N(SiMe₃)₂}(NCR)]₂ [R = Ad (1a) or Bu^t (1b)], trans-[Na{µ-N(SiMe₃)(SiMe₂Ph)}(NCR)]₂ [R = Ad (2a) or Bu^t (2b)], [(Na{µ-N(SiMe₃)Bu^t})₃(NCAd)₃] (3a) or [(Na{µ-N(SiMe₃)Bu^t})₃(NCBu^t)_n] [n = 3 (3b) or 2 (3c)] was isolated. The reaction of complexes 3a or 3b with benzene afforded the ketimido complex [Na{µ-NC(Ad)(Ph)}]₆·2C₆H₆ (4a) or [Na{µ-NC(Bu^t)(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{µ-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.