219927-86-3Relevant academic research and scientific papers
Attachment of the new bulky ligand (Me3Si)2(Me2NMe2Si)C to Li, Hg, Al, Ga, and Sn. (see abstract)
Al-Juaid, Salih S.,Eaborn, Colin,El-Hamruni, Salima M.,Hitchcock, Peter B.,Smith, J. David
, p. 45 - 52 (1999)
The organolithium reagent [Li{C(SiMe3)2(SiMe2NMe2)(THF) 2] (1) is readily obtained by reaction of the chloride (Me3Si)2(Me2NMe2Si)CCl with LiBu in THF (tetrahydrofuran) at low temperature. Reactions of 1 with HgBr2, AlCl3, GaCl3, and SnCl4 give [Hg{C(SiMe3)2-(SiMe2NMe2)} 2] (2), [Al{C(SiMe3)2(SiMe2NMe2)}Cl 2)] (3), Ga{C(SiMe3)2(SiMe2NMe2)}Cl 2 (5), and [Sn{C(SiMe3)2(SiMe2NMe2)}Cl 3] (6), respectively, and treatment of 3 with LiPh gives [Al{C(SiMe3)2(SiMe2NMe2)}Ph 2] (4). Crystal structure determinations have shown that there is intramolecular coordination of the N atom to the metal M, with formation of a planar four-membered C-Si-N-M ring, in 1, 3, 4, and 5 (but not 2). Engagement of the lone pair on N in coordination with Al in 3 results in an exceptionally long Si-N bond length of 1.875-(2) A, some 0.16 ? longer than that in 2 and in simple silylamines generally; the Si-N bond is possibly shorter in 4 (1.851(2) ?) and 5 (1.858(4) ?), and is markedly so in 1 (1.796(4) ?), but still notably long. The lengths of the N - metal bonds in these compounds are similar to those between alkylamines and the metals in coordination compounds, indicating that at least in these systems the N atoms in the silylamines coordinate as strongly as those in the organic amines. Reaction of 6 with MeOH occurs exclusively at the Si-N bond to give [Sn-{C(SiMe3)2(SiMe2OMe)}Cl3], that of 2 with ICI or CF3CO2H gives [Hg{C(SiMe3)2(SiMe2Cl)}2] and [Hg{C(SiMe3)2(SiMe2O2CCF 3)}2], respectively, and that of 1 with ICH2CH2I gives the iodide (Me3Si)2(Me2NMe2Si)CI.
