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

Reactions between sodium amides Na[N(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{µ-N(SiMe3)2}(NCR)]2[R = Ad (1a) or But(1b)], trans-[Na{µ-N(SiMe3)(SiMe2Ph)}(NCR)]2[R = Ad (2a) or But(2b)], [(Na{µ-N(SiMe3)But})3(NCAd)3] (3a) or [(Na{µ-N(SiMe3)But})3(NCBut)n] [n= 3 (3b) or 2 (3c)] was isolated. The reaction of complexes 3aor 3bwith benzene afforded the ketimido complex [Na{µ-NC(Ad)(Ph)}]6·2C6H6(4a) or [Na{µ-NC(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{µ-N(SiMe3)2}(NCAd)]2(5a), is also presented. The compounds 1a, 1b, 2a, 2b, 3, 3b, 4a, 4band 5awere characterised by X-ray diffraction.