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1988 (2)
1Author    M. Veith, J. PöhlmannRequires cookie*
 Title    Nitrogen Compounds of Elements of the Third Main Group with Intra-and Intermolecular Donor Acceptor Bonds, V [1] Special Gallium and Indium Amides with Alkoxo Groups  
 Abstract    The lithium alkoxoamidosilane (Me2Si(O r Bu)(N r Bu)Li)2 (4) and its trimethyltin derivative Me2Si(0'Bu)(N'Bu)SnMe3 (7) have been used, to introduce the ligand Me2Si(0'Bu)(N'Bu) = L into molecular compounds of gallium and indium. The following molecules were synthesized: L—M(Me)Cl (M = Ga (5), In (6)), L-InMe2 (8), L-InX2 (X = Cl (9), Br (10)), L2InX (X = Cl (11), Br (12)) and L2Ga2Cl2 (22). The ligand L is assumed to chelate the metal atom on the basis of temperature dependent 'H NMR spectra. The chelating effect is more pronounced in the gallium derivatives than in the indium analogues. Equilibria between L2InX/InX, and LInX: have been observed in diethylether solutions. No metal(I) derivatives LGa or Lin could be isolated. L2Ga2Cl2 (22), formally containing gallium(ll), can be sublimed without decomposition at 110 °C in vacuo. 
  Reference    Z. Naturforsch. 43b, 505—512 (1988); eingegangen am 28. Dezember 1987 
  Published    1988 
  Keywords    Synthesis, Chelated Metal Atoms, Intramolecular Rearrangements, Equilibria Followed by 'H NMR 
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 TEI-XML for    default:Reihe_B/43/ZNB-1988-43b-0505.pdf 
 Identifier    ZNB-1988-43b-0505 
 Volume    43 
2Author    M. Veith, F. Goffing, V. HuchRequires cookie*
 Title    On the Coordination of Different Main Group Metals with a Special, Chelating Silazane  
 Abstract    The c/s-isomer of the silazane H ; L (1) (L = [N'Bu][Me]Si(N r Bu) 2 Si[Me][N r Bu]) has been used as a ligand to main group metals. By displacing the hydrogen atoms of 1 the compounds L(MgMe) 2 (4), L(MgCl) 2 (5) and L(Li)(InMe 2) (6) have been obtained. According to the 'H NMR spectra the structures of 4—6 are very similar: a polycyclic, cubane-like Si 2 N 4 M 2 framework results from the special atomic arrangements and from intramolecular Lewis acid-base interactions between the metals M and the nitrogen atoms. Divalent metals and metal-centered groups can also be incorporated into 1. In the latter case a seco norcubane-like polycycle Si 2 N 4 M is produced as confirmed by X-ray structure determinations of LGaMe (8) and LSb + InCl 4 ~ (11). LInMe (7) and LSn (9) seem to adopt the same tricyclic structure as 8, although the 'H NMR spectra are not consistent with a rigid molecule (low symmetry), but rather with a fluxional behaviour (high symmetry). When 5 is allowed to react with sodium/naphthalene in THF part of the magnesium is reduced and LMg(THF) : (12) is formed. An X-ray structure determination of 12 reveals the compound to be only bicyclic with the magnesium atom coordinated by two nitrogen and two THF oxygen atoms. 
  Reference    Z. Naturforsch. 43b, 846—856 (1988); eingegangen am 8. Februar 1988 
  Published    1988 
  Keywords    Metal Amides, Molecular Structures, 'H NMR Spectra X-Ray, Chelated Metal Atoms 
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 TEI-XML for    default:Reihe_B/43/ZNB-1988-43b-0846.pdf 
 Identifier    ZNB-1988-43b-0846 
 Volume    43