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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 2579-2584 
    ISSN: 0009-2940
    Keywords: Aluminosiloxanes ; 1,3-Diorganodisiloxanes ; Siloxane cleavage by aluminium halides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: sym-Diorganodisiloxanes RH2SiOSiH2R (R = C2H5, 7; C2H3, 8; C2H, 9) are prepared by hydrolysis of organo(bromo)silanes which are available in high yields by the reaction of organo-(phenyl)silanes with liquid HBr. Asymmetrical cleavage of these disiloxanes with AlCl3 leads to the formation of organo-(chloro)silanes and aluminosiloxane dimers [RH2SiOAlCl2]2 (R = C2H5, 10; C2H3, 11; C2H, 12). Crystal structure determinations of 11 and 12 reveal a planar centrosymmetrical SiOAl2OSi skeleton with three-coordinate oxygen atoms and tetrahedral four-coordinate aluminum atoms. Treatment of 7-9 with Me2AlCl yields volatile dimethylaluminumorganosilyl oxides [RH2SiOAlMe2]x (R = C2H5, 13; C2H3, 14; C2H, 15; x = 2, 3, 4). NMR studies confirm the presence of more than one oligomer in solutions of these compounds. The asymmetrical compound (HC-CSiH2O)2Me3Al2Cl (16), resulting from small amounts of MeAlCl2 in the Me2AlCl used, is isolated as a byproduct in the synthesis of 15. The crystal structure of 16 shows a disorder of the molecules leading to pseudosymmetry with a center of inversion.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 2027-2032 
    ISSN: 0009-2940
    Keywords: Silylamines ; Silazanes ; Nitrogen configuration ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and characterization of two complete series of benzyl(phenylsilyl)amines (PhH2Si)x(PhH2C)3  -  xN, benzyl(p-tolylsilyl)amines (p-H3CC6H4H2Si)x(PhH2C)3  -  xN, and of bis-(p-tolylsilyl)amine are described. The compounds have been prepared from the corresponding amines and chlorosilanes with triethylamine as the auxiliary base. Bis(phenylsilyl)(trimethylsilyl)amine, (PhH2Si)2NSiMe3 (10), was obtained by the reaction of lithium bis(phenylsilyl)amide with chlorotrimethylsilane. Crystal structure analyses reveal that dibenzyl(p-tolylsilyl)amine (7) and 10 contain planar nitrogen atoms. Heteronuclear NMR spectra (1H, 13C, 15N, and 29Si) have been measured for all compounds. The 15N chemical shifts are shown to be sensitive to variations of the geometry at the nitrogen atom. The coupling constants 1J(15N29Si) show a linear correlation with the N - Si bond lengths.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0044-2313
    Keywords: Gold(I) benzenedithioles ; Gold(III) benzenedithioles ; (Phosphine)gold(I) complexes ; Benzenedithiolato complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: (Phosphan)gold(I)-Komplexe von Benzoldithiolen Kristallstruktur des 1,2-Benzoldithiolato-bis[triphenylphosphan-gold(I)] und Bis(triethylphosphan)gold(I)-bis(1,2-benzoldithiolato)gold(III)Die Reaktionen von 1,2- und 1,3-Benzoldithiol mit Chloro(phosphan)gold(I)-Komplexen R3PAuCl (R = Et, Ph) in Gegenwart von Triethylamin in Tetrahydrofuran ergeben in hohen Ausbeuten die stabilen Gold(I)-Komplexe 1,2-C6H4(SAuPR3)2 [R = Et (1) und Ph (2)] bzw. 1,3-C6H4(SAuPPh3)2 (3). Die Verbindungen wurden durch analytische und NMR-spektroskopische Daten charakterisiert. Aus der Reaktion von 1,2-C6H4(SH)2 mit Et3PAuCl wurde in geringer Ausbeute auch die Verbindung [(Et3P)2Au]+ [Au(1,2-C6H4S2)2]- (4) isoliert. Die Kristallstrukturen der Verbindungen 2 und 4 wurden durch Einkristall-Röntgenstrukturanalysen bestimmt. Die Goldatome in Komplex 2 sind zweifach koordiniert mit Bindungswinkeln S—Au—P von 175,2(1) und 159,5(1)°, Au - S-Bindungslängen von 2,304(1) und 2,321(1) Å und kurzen Au-Kontakten von 3,145(1) Å. Die Goldatome im Kation des Komplexes 4 sind ebenfalls linear zweifach koordiniert mit einem P - Au - P-Winkel von 170,1(1)° und Au - P-Abständen von 2,296(3) und 2,298(3) Å. Die Geometrie des Anions weist eine quadratisch-planare Umgebung des Gold(III)-Zentrums auf mit zwei chelatisierenden 1,2-Benzoldithiolat-Liganden, deren Au—S-Abstände zwischen 2,299(3) und 2,312(3) Å liegen (zwei kristallographisch unabhängige, centrosymmetrische Anionen in der Elementarzelle).
    Notes: The reaction of 1,2- and 1,3-benzenedithiol C6H4(SH)2 with chloro(phosphine)gold(I) complexes R3PAuCl (R = Et, Ph) in the presence of triethylamine in tetrahydrofuran gives stable gold(I) complexes 1,2-C6H4(SAuPR3)2 [R = Et (1) and Ph (2)] or 1,3-C6H4(SAuPPh3)2 (3), respectively, in high yield. The compounds have been characterized by analytical and NMR spectroscopic data. From the reaction of 1,2-C6H(SH)2 with Et3P—AuCl a by-product [(Et3P)2Au]+ [Au(1,2—C6H4S2)2]- (4) has also been isolated in low yield. The crystal structures of compounds 2 and 4 have been determined by single crystal X-ray diffraction. The gold(I) atoms in complex 2 are two-coordinate with bond angles S—Au—P of 175.2(1) and 159.5(1)°, Au—S bond distances of 2.304(1) and 2.321(1) å, and a short Au…Au contact of 3.145(1) Å. The gold(I) atom in the cation of complex 4 is also linearly two-coordinate with a P—Au—P angle of 170.1(1) Å and Au—P distances of 2.296(3) and 2.298(3) Å. The geometry of the anion in 4 shows a square-planar coordination of gold(III) by two chelating 1,2-benzenedithiolate ligands with Au—S distances between 2.299(3) and 2.312(3) Å (for two crystallographically independent, centrosymmetrical anions in the unit cell).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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