13307-05-6Relevant articles and documents
Aminolysis of the Si-Cl bond and ligand exchange reaction between silicon amido derivatives and SiCl4: Synthetic applications and kinetic investigations
Passarelli, Vincenzo,Carta, Giovanni,Rossetto, Gilberto,Zanella, Pierino
, p. 413 - 419 (2003)
The aminolysis of the Si-Cl bond in SiCln(NR2)4-n (n = 1, 2, 3, 4) has been employed for the synthesis of binary amido, chloro-amido or mixed amido derivatives, depending on the nature of the silicon derivative and of the
Non-oxide sol-gel chemistry: Preparation from tris(dialkylamino)silazanes of a carbon-free, porous, silicon diimide gel
Rovai, Riccardo,Lehmann, Christian W.,Bradley, John S.
, p. 2036 - 2038 (1999)
The acid-catalyzed ammonolysis of the hitherto unknown compound tris(dimethylamino)silylamine (1), which is prepared from SiCl4 in high yield and purity, results in the preparation of a silicon diimide gel. The probable first step in this proce
Syntheses and structures of [(Me3N)3SiNHLi] 4, (C4H8O)Al[NHSi(NMe2) 3]3, ((Me2N)3SiNH)3Al and Li(THF)2+[((Me2N)3SiNH) 4Al]-
Bradley, John S.,Cheng, Fei,Archibald, Stephen J.,Supplit, Ralf,Rovai, Riccardo,Lehmann, Christian W.,Krueger, Carl,Lefebvre, Frederic
, p. 1846 - 1851 (2003)
The preparation of lithium tris(dimethylamino)silylamide, [(Me 3N)3SiNHLi]4, 2, and its reaction with aluminium trichloride to give tris(dimethylamino)silylamino)(tetrahydrofuran) alane, (C4H8O)Al[NHSi(NMe2)3] 3, 3, and bis(tetrahydrofuran)lithium tetrakis(tris(dimethylamino) silylamino)alanate, Li(THF)2+[((Me2N) 3SiNH)4Al]-, 6, is reported, together with the crystal structures of 2, 3 and 6. Tris(dimethylamino)alane, ((Me 2N)3SiNH)3Al, was obtained by reaction of tris(dimethylamino)silylamine with aluminium triethyl. The ammonolytic gelation of 3 to an imidoaluminosilicate gel is also described. The Royal Society of Chemistry 2003.
Synthesis of 1,4-disilacyclohexa-2,5-dienes
Yang, Jinchao,Guzei, Ilia,Verkade, John G
, p. 276 - 288 (2007/10/03)
Title compounds of the type 2,3,5,6-tetraphenyl-1,4-di-X-1,4-di-Y-1,4-disilacyclohexa-2,5-diene wherein X = Y = NMe2 (4); X = NMe2, Y = Cl (cis, trans-5); X = NMe2, Y = Me [(trans)-6] and X = t-Bu, Y = Cl (trans-8) were synthesized from Si2(NMe2)5Cl, sym-Si2(NMe2)4Cl2, sym-Si2(NMe2)4Me2, and sym-Si2Cl4(t-Bu)2, respectively, in the presence of diphenylacetylene at 200 °C. Similarly the analogous title compound from the combination of 1-phenyl-1-propyne and Si2(NMe2)5Cl [X = Y = NMe2 (cis and trans-7) was synthesized. In all cases where cis/trans diastereomers could arise from two different silicon substituents (5, 6, 8) the trans isomer was the sole or dominant product. Evidence for the intermediacy of the silylene Si(NMe2)2 in these reactions was gained from a trapping experiment. Compound 4 upon treatment with SiCl4, SiBr4 or PI3 provided the corresponding 1,1,4,4-tetrahalo derivatives 9a-c, respectively. Treatment of 4 with MeOH or PhOH gave the 1,1,4,4-tetramethoxy and tetraphenoxy analogues 9d and 9e, respectively. The tetrachloro derivative 9a upon LAH reduction led to the corresponding tetrahydro compound 10, while the reaction of 9a with H2O gave the tetrahydroxy derivative 11. Allowing (trans)-6 to react with SiCl4 provided a ca. 1:1 cis/trans ratio of the derivative 12 in which X = Cl, Y = Me, and possible pathways that rationalize this loss of stereochemistry are proposed. Synthesis of trans-13 in which X = t-Bu, Y = H was achieved by LAH reduction of 8. All of the title compounds except 8 experience free phenyl rotation at room temperature. At - 30 °C this rotation in 8 is essentially halted. The molecular structures of 4, 8, 9c, 9e, 10 and 13 were determined by X-ray crystallography.
Complexation and Exchange Reactions of some Dimethylamino-substituted Group 4 Compounds
Wade, Steven R.,Willey, Gerald R.
, p. 1264 - 1267 (2007/10/02)
Reactions of CH2(NMe2)2, (1), SiMe2(NMe2)2, (2), (cp=η-cyclopentadienyl), (3), and , (4), with covalent metal halides MCl4 (M=Ti,Zr,Si,Ge,or Sn) and MCl3 (M=Ti,V,or Cr) fall into two categories: (a) N-donor chelation leading to complex formation and (b) halide-NMe2 exchange.Compound (1) gives 1:1 complexes with MCl4 (M=Ti or Sn) and 2:1 complex with VCl3.Compound (2) provides 1:1 complexes with MCl4 (M=Ti,Zr,Hf, or Sn).The decomposition of TiCl4*SiMe2(NMe2)2 --> invariably occurs in both the solid state and solution.There is no reaction of (2) with metal(III) chlorides.With MCl4 (M=Si or Ge 'scrambling' reactions involving halide-NMe2 exchange occur and these have been monitored by 1H n.m.r. spectroscopy.Reactions of (3) and (4) with MCl4 (M=Si,Ge,Sn,Ti,Zr,or Hf) consistently feature halide-NMe2 exchange rather than adduct formation.All complexes have been characterised by analytical and spectroscopic (1H n.m.r. and i.r.) investigations.
