Synthesis and structures of crystalline Li, Al and Sn(II) 1-azaallyls and beta-diketiminates derived from [Li{mu,eta3-N(SiMe3)C(Ad)C(H)SiMe3}]2 (Ad = 1-adamantyl)

The crystalline dimeric 1-azaallyllithium complex Li{mu,eta(3-N(SiMe3)C(Ad)C(H)SiMe3}]2 (1) was prepared from equivalent portions of LiCH(SiMe3)2] and 1-cyanoadamantane (AdCN). Complex was used as precursor to each of the crystalline complexes 2-8 which were obtained in good yield. By 1-azaallyl ligand transfer, 1 afforded (i) Al{eta3-N(SiMe3)C(Ad)C(H)SiMe3}{kappa1-N(SiMe3)C(Ad)=C(H)SiMe3-E}Me] (5) with AlCl2Me](2), (ii) Sn{eta3-N(SiMe3)C(Ad)C(H)SiMe3}2] (7) with SnN(SiMe3)2]2, and (iii) Li(N{C(Ad)=C(H)SiMe3-E}{Si(NN)SiMe3})(thf)2] (8) with the silylene Si(NCH(2)Bu(t))2C6H(4)-1,2] = Si(NN)]. By insertion into the Ctriple bond, length as m-dash]N bond of the appropriate cyanoarene RCN, gave the beta-diketiminate Li{mu-N(SiMe3)C(Ad)C(H)C(R)NSiMe3}]2 R = Ph (2), C(6)H(4)Me-4 (3)], and yielded Al{kappa2-N(SiMe3)C(Ad)C(H)C(Ph)NSiMe3}{kappa1-N(SiMe3)C(Ad)=C(H)SiMe3-E}Me] (6). The beta-diketiminate Al{kappa2-N(SiMe3)C(Ad)C(H)C(Ph)NSiMe3}Me2] (4) was prepared from 2 and AlClMe2]2. The X-ray structures of 1 and 3-8 are presented. Multinuclear NMR spectra in C6D6 or C6D5CD3 have been recorded for each of 1-8; such data on 8 revealed that in solution two minor isomers were also present.