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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 365-371 
    ISSN: 0009-2940
    Keywords: Cumulenes ; Butadienes ; Vinylcyclopropane ; Vinylidenecyclopropane ; Bicyclopropyl, phosphanyl-substituted ; Cyclopropanation ; Phosphane ligands ; Phosphane chalcogenides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydrophosphorylation of 1,4-bis(diphenylphosphanyl)butadiyne with diphenylphosphane leads to the butadiene (Ph2P)2C=CH—CH=C(PPh2)2 (1). Treatment of 1 with dimethylsulfonium methylide gives the vinylcyclopropane (Ph2P)2C=CH—CH(CH2)C(PPh2)2 (2). Compound 2 reacts with aqueous hydrogen peroxide, elemental sulfur, or selenium to afford the tetrachalcogenides (Ph2XP)2C=CH—CH(CH2)C(PXPh2)2 with X = O (3), X = S (4), X = Se (5), respectively. While the tetraphosphane 1 and the vinyl-cyclopropane compound 2 cannot be converted into a bis-(cyclopropyl) compound with an excess of Me2S=CH2, the tetrasulfide 4 readily affords a mixture of (1R,1′R)-/(1S,1′S)-and meso-2,2,2′,2′-tetrakis(diphenylthiophosphinyl)-1,1′-bicyclopropyl (6, 7) in good yield. Treatment of 1,1,4,4-tetrakis-(diphenylphosphanyl)butatriene with dimethylsulfonium methylide leads to the vinylidenecyclopropane (Ph2P)2C=C=C(CH2)C(PPh2)2 (8). Compound 8 is converted into its tetrasulfide (Ph2SP)2C=C=C(CH2)C(PSPh2)2 (9) by treatment with elemental sulfur. The crystal structures of 1, 2, 4, 7, and 8 have been determined by single-crystal X-ray diffraction.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    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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