Synthesis and structures of crystalline Li, Al and Sn(II) 1-azaallyls and beta-diketiminates derived from [Li{mu,eta(3)-N(SiMe3)C(Ad)C(H)SiMe3}](2) (Ad = 1-adamantyl)

摘要

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 Li[CII(SiMe3)(2)] and 1-cyanoadamantane (AdCN). Complex 1 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{eta(3)-N(SiMe3) C(Ad)C(H)SiMe3}{kappa(1)-N(SiMe3)C(Ad)=C(H)SiMe3-E} Me] (5) with [AlCl2Me](2), (ii) [Sn{eta(3)-N(SiMe3)C(Ad)C(H)SiMe3}(2)] (7) with Sn[N(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)But) 2C6H4-1,2] [= Si(NN)]. By insertion into the C=N bond of the appropriate cyanoarene RCN, 1 gave the beta-diketiminate [Li{mu-N(SiMe3)C(Ad)C(H)C(R)NSiMe3}](2) [R = Ph (2), C6H4Me-4 (3)], and 5 yielded [Al{kappa(2)-N(SiMe3C(Ad)C(H)C(Ph)NSiMe3}{kappa(1)-N(SiMe3) C(Ad)= C(H)SiMe3-E}Me] (6). The beta-diketiminate [Al{kappa(2)-N(SiMe3) C(Ad) C(H) C(Ph) NSiMe3}Me-2] (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.