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2001 (1)
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1Author    EvaS. Schmidt, Annette Schier, NorbertW. Mitzel, Hubert SchmidbaurRequires cookie*
 Title    A Simple High-Yield Synthesis of Gallium(I) Tetrachlorogallate(III) and the Reaction of Digallium Tetrachloride Tetrahydrofuran Solvate with 1,2-Diols  
 Abstract    Gallium(I) tetrachlorogallate(III) Ga[GaCU] was prepared in quantitative yield by thermal de­ composition of dichlorogallane [HGaChk, which is readily available from EtsSiH and [GaCl3]2. The reaction of catechol with solutions of this gallium(I) tetrachlorogallate(III) in tetrahydro­ furan leads to the evolution o f hydrogen gas and affords a dinuclear gallium(III) complex with penta-coordinate metal atoms chelated and bridged by mono-deprotonated catechol ligands. In the crystalline phase tetrahydrofuran molecules are hydrogen-bonded to the hydroxy groups: [G a(l,2 -0 CöH4 0 H)Cl2(C4H8 0)]2. The reaction with pinacol also gives hydrogen and the anal­ ogous product [Ga(0 CMe2CMe2 0 H)Cl2(C4Hg0)]2. The structures of the two compounds have been determined by X-ray diffraction. A mechanism of the new reaction has been proposed which involves oxidative addition of the diol to the solvate (THF)Cl2Ga-GaCl2(THF) present in the tetrahydrofuran solution to give a gallium hydride intermediate. 
  Reference    Z. Naturforsch. 56b, 337—341 (2001); received March 23 2001 
  Published    2001 
  Keywords    Gallium Halides, Gallium Diolates, Oxidative Addition 
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 TEI-XML for    default:Reihe_B/56/ZNB-2001-56b-0337.pdf 
 Identifier    ZNB-2001-56b-0337 
 Volume    56 
2Author    Christoph Kümmel, Anton Meller, Mathias NoltemeyerRequires cookie*
 Title    Intramolekular-stabilisierte Organogallium-und -indiumhalogenide. Ein erstes neutrales Indiumhydrid Intramolecularly Stabilized Organogallium-and -indium Halides. A First Neutral Indium Hydride  
 Abstract    The intramolecularly coordinating 2-(dimethylaminomethyl)phenyl-(X) and 4-terr-butyl-2,6-bis(dimethylaminomethyl)phenyl-(Y) ligands were employed in the preparation of the gallium and indium halides: X2InI (B), XInI2 (1), X2InBr (2), XInBr2 (3), XIn(Et)I (4), XGaI2 (6) and YInI2 (7). The first neutral indium hydride X2InH (5) was made in situ from LiInH4 and 2. Z2InCl (8) (Z = 2-pyridyl-bis(trimethylsilyl)methyl), and X3Ga (C) were also synthesized. The compounds are characterized by N. M. R. ('H, 13C, 29Si and for 6 71Ga) and mass spectrometry and elemental analyses or peak matching M. S.. N. M. R.-data are discussed as well as the X-ray structure analyses provided for B, 2, 4, 5, 7 and 8. 
  Reference    Z. Naturforsch. 51b, 209—219 (1996); eingegangen am 13. Juli 1995 
  Published    1996 
  Keywords    Gallium Halides, Indium Halides, Gallium Aryls, Indium Aryls, Aryl Indium Hydride 
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 TEI-XML for    default:Reihe_B/51/ZNB-1996-51b-0209.pdf 
 Identifier    ZNB-1996-51b-0209 
 Volume    51 
3Author    Marcus Sigl, Annette Schier, Hubert SchmidbaurRequires cookie*
 Title    Lewis Acid Catalyzed Z to E Isomerization of 1,2-Bis(diphenyl- phosphino)ethene  
 Abstract    Z-l,2-Bis(diphenylphosphino)ethene, cis-Ph2PCH=CHPPh2, forms 1:2 adducts with GaBn and GaL, the former of which has been identified in an X-ray diffraction study as the complex of the isomerized ligand, E-Ph2PCH=CHPPh2. The GaL complex is believed to be analogous on the basis of analytical and spectroscopic data. InBr3 affords a 1 :1 complex with an ionic structure [(Ph2PCH=CHPPh2)2lnBr2]+ [InBr4]_ in which the cation contains the original cis-ligand. With Inl^ also a 1:1 adduct is obtained, where the metal triiodide unit is attached to only one phosphorus atom of the non-isomerized (cis) ligand in the solid state. There is rapid site exchange of the Inl3 unit in chloroform solution as followed by NMR spectroscopy. -The metal halide induced Z/E isomerization of Ph2PCH=CHPPh2 has been studied in various solvents and at variable temperature with stoichiometric and catalytic amounts of AIX3 and GaX3 Lewis-acids. InX3 compounds proved ineffective (X = Cl, Br, I). Anhydrous AlBr3 was found to be most efficient, giving a 90% Z/E conversion in 10 min at 100°C in toluene. A mechanism is proposed which is compatible with the experimental data. 
  Reference    Z. Naturforsch. 53b, 1301—1306 (1998); received August 13 1998 
  Published    1998 
  Keywords    Z/E Isomerization, Phosphino-Ethenes, Lewis Acid Catalysis, Gallium Halides, Aluminium Halides, Indium Halides 
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 TEI-XML for    default:Reihe_B/53/ZNB-1998-53b-1301.pdf 
 Identifier    ZNB-1998-53b-1301 
 Volume    53