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1999 (2)
1998 (1)
1Author    Z. NaturforschRequires cookie*
 Title    Pentacoordinated Nitrogen Atoms in the Structure of Hexalithium Bis[methylsilyl-tris(methylimide)] Hexakis(tetrahydrofuran)  
 Abstract    Lithiation of tris(methylamino)wt'f/7v/silane using an excess of n -butyllithium affords the cor­ responding trifunctional lithium amide in high yield. The compound crystallizes from tetrahy-drofuran as a dimer with six donor molecules: {[M eSi(NM eLi)3]2(thf)6}. The cluster is a cage structure grouped around a crystallographic center of inversion. The silicon and lithium atoms are tetrahedrally tetracoordinated, but the nitrogen atoms are pentacoordinated and have a square pyramidal environment of one carbon, one silicon, and three lithium atoms. Parallels can be drawn to other species with polymetallated nitrogen functions. An analogous compound was prepared from tris(methylamino)vwv/silane. 
  Reference    (Z. Naturforsch. 54b, 8—12 [1999]; received September 1 1998) 
  Published    1999 
  Keywords    Silylamines, Silylamides, Crystal Structure 
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 TEI-XML for    default:Reihe_B/54/ZNB-1999-54b-0008.pdf 
 Identifier    ZNB-1999-54b-0008 
 Volume    54 
2Author    Gerald Huber, Hubert SchmidbaurRequires cookie*
 Title    The Basicity of Silylamines and Alkylamines: An Equilibrium Study of the Competitive Borane Adduct Formation  
 Abstract    In order to investigate the Lewis acid/base chemistry of silylamines in solution, the equilib­ rium reactions of MeßSiNMea / Me3SiNMe2(BH3) and different amines NR3 / amineboranes NR3(BH3) were monitored by 'H NMR spectroscopy in CöDö and CDCI3 at 60 °C. For the equilibrium of the reference silylamine/-borane and Me3CNMe2 / Me3CNMe?(BH3) values K = 0.35 (A G = 3.1 kJ m o P ') in C6D6 and K = 0.50 (A G = 2.0 kJ m o r T) in CDC13 have been estimated, showing that both the silylamine and the C/Si-analogous organic amine have very similar donor properties. Small amines like NMe3 proved to be much more powerful donors than the silylamine Me3SiNMe2, whereas bulky amines are less efficient donors, indicating that steric effects play an important role. The formation of BH3 adducts of Me2NSiH3 and (H3Si)3N which could not be followed experimentally owing to the low stability of the products, has been studied by quantum chemical calculations. A comparison with data for Me3N(BH3) shows that the silylamines are poorer donors, but the reason for this remains unclear. 
  Reference    Z. Naturforsch. 53b, 1103—1108 (1998); received July 21 1998 
  Published    1998 
  Keywords    Silylamines, Alkylamines, Borane Adducts, Amineboranes, Basicity Studies 
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 TEI-XML for    default:Reihe_B/53/ZNB-1998-53b-1103.pdf 
 Identifier    ZNB-1998-53b-1103 
 Volume    53 
3Author    Z. NaturforschRequires cookie*
 Title    The Stereochemistry of Chloro-bis(N-morpholino)phenylsilane  
 Abstract    Treatment of phenyltrichlorosilane with an excess of morpholine and N-lithium-morpholide in pentane/toluene affords only the disubstitution product Cl(Ph)Si(M or)2 with Mor = 0 (C H 2C H :)2N-. The third halogen atom is not replaced owing to sterical hindrance. The title compound crystallizes with two independent molecules in the unit cell. These two molecules can be classified as enantiomers, because a disrotatory twist of the two morpholino ligands away from the potential mirror plane induces a chiral conformation. In benzene solution there is racemization owing to completely free rotation, chair/boat interconversion, and nitrogen inversion of the morpholino groups on the NMR time scale, but all CH 2 protons remain anisochronous (diastereotopic). 
  Reference    (Z. Naturforsch. 54b, 18—20 [1999]; received October 15 1998) 
  Published    1999 
  Keywords    Silylamines, Aminosilanes, Symmetry, NMR Data, Crystal Structure 
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 TEI-XML for    default:Reihe_B/54/ZNB-1999-54b-0018.pdf 
 Identifier    ZNB-1999-54b-0018 
 Volume    54