Synthesis and structures of crystalline Li, Al and Sn(ii) 1-azaallyls and beta-diketiminates derived
June 28th, 2008 | by admin |Synthesis and structures of crystalline Li, Al and Sn(ii) 1-azaallyls and beta-diketiminates derived from [Li{mu,eta(3)-N(SiMe(3))C(Ad)C(H)SiMe(3)}](2) (Ad = 1-adamantyl).
The crystalline dimeric 1-azaallyllithium complex [Li{mu,eta(3)-N(SiMe(3))C(Ad)C(H)SiMe(3)}](2) () was prepared from equivalent portions of Li[CH(SiMe(3))(2)] and 1-cyanoadamantane (AdCN). Complex was used as precursor to each of the crystalline complexes which were obtained in good yield. By 1-azaallyl ligand transfer, afforded (i) [Al{eta(3)-N(SiMe(3))C(Ad)C(H)SiMe(3)}{kappa(1)-N(SiMe(3))C(Ad)[double bond, length as m-dash]C(H)SiMe(3)-E}Me] () with [AlCl(2)Me](2), (ii) [Sn{eta(3)-N(SiMe(3))C(Ad)C(H)SiMe(3)}(2)] () with Sn[N(SiMe(3))(2)](2), and (iii) [Li(N{C(Ad)[double bond, length as m-dash]C(H)SiMe(3)-E}{Si(NN)SiMe(3)})(thf)(2)] () with the silylene Si[(NCH(2)Bu(t))(2)C(6)H(4)-1,2] [= Si(NN)]. By insertion into the C[triple bond, length as m-dash]N bond of the appropriate cyanoarene RCN, gave the beta-diketiminate [Li{mu-N(SiMe(3))C(Ad)C(H)C(R)NSiMe(3)}](2) [R = Ph (), C(6)H(4)Me-4 ()], and yielded [Al{kappa(2)-N(SiMe(3))C(Ad)C(H)C(Ph)NSiMe(3)}{kappa(1)-N(SiMe(3))C(Ad)[double bond, length as m-dash]C(H)SiMe(3)-E}Me] (). The beta-diketiminate [Al{kappa(2)-N(SiMe(3))C(Ad)C(H)C(Ph)NSiMe(3)}Me(2)] () was prepared from and [AlClMe(2)](2). The X-ray structures of and are presented. Multinuclear NMR spectra in C(6)D(6) or C(6)D(5)CD(3) have been recorded for each of ; such data on revealed that in solution two minor isomers were also present.
Bourget-Merle L, Hitchcock PB, Lappert MF, Merle PG.
Department of Chemistry, University of Sussex, Brighton, United KingdomBN1 9QJ. m.f.lappert@sussex.ac.uk.