The Thermally Stable Silylene Si[(NCH2But)2C6H4‐1,2]: Reactions with ButCN,AdCN, ButNC,AdN3, and Me3SiN3 (Ad = 1‐Adamantyl)

The crystalline compounds NSi(NN)Si(NN)CR R = Bu^t ( 2 a ), Ad ( 2 b )], (NN)Si(Bu^t)CN ( 3 ), Bu^tSi(NN)Si(NN)CN ( 4 ), AdNSi(NN)Si(NN) ( 5 ), AdNN=NN(Ad)Si(NN) ( 6 ), (NN)Si(N₃)N(SiMe₃)₂ ( 7 ) and Me₃SiNSi(NN)Si(NN)(thf) ( 8 ) were obtained in good yield under mild conditions from Si(NCH₂Bu^t)₂C₆H₄‐1,2] ≡ Si(NN)] and the appropriate reagent RCN, Bu^tNC and R′N₃. The compounds 2 – 8 were characterised by microanalysis, multinuclear NMR and (not 8 ) mass spectra, as well as for 2 a , 4 and 7 single crystal X‐ray diffraction data. The results are placed in context of data in the literature on reactions of especially SiN(Bu^t)CH=]₂, (SiBu^t₂)₃, Mes₂Si=SiMes₂ with (where available) a nitrile, isonitrile or azide. Reaction pathways are discussed.