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  • 1
    ISSN: 0044-2313
    Keywords: Mononuclcar scfonolato tungsten complexes ; binuclear selenolato complexes ; 77Se-NMR ; x-ray structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Complexing Properties of Organometallic Selenolato Complexes. The Crystal Structures of [cp(CO)3W(μ-SeCH2Ph)W(CO)5], [cp(CO)3W(μ-SeCH2Ph)Cr(CO)5], [cp(CO)3W(μ-SeCH2Ph)Fe(CO)2cp]+ClO4-, and [cp(CO)3W(μ-SeCH2SiMe3)AuPPh3]+SbF6-The reaction of the selenolato tungsten complexes cp(CO)3WSeR; R = CH2Ph, CH2SeSiMe3, with the unsaturated complexes M(CO)5(THF); M = Cr, W or the complex cations Ph3PAu+ and cp′(CO)2Fe+; cp′ = C5H5, C5Me5, forms binuclear complexes, in which selenium possesses a formal positive charge. The crystal structures of the compounds 1, 2, 4 und 8 were determined by X-ray single crystal structure analysis (1: space group P212121 (Nr. 19), Z = 16, a = 1744.5(3) pm b = 2079.5(3) pm, c = 2435.7(5) pm; 2: space group P1 (Nr. 2), Z = 8, a = 1318.94(14) pm, b = 1732.5(2) pm, c = 2119.9(2) pm, = 89.805(10)°, β = 86.586(10)°, γ = 68.731(10)°; 4: space group P1 (Nr. 2), Z - 2, a = 828.0(5) pm, b = 1027.4(5) pm, c = 1510.8(9) pm, α = 109.84(3)°, β = 99.45(4)°, γ = 91,43(3)°; 8: space group P1 (Nr. 2), Z = 4, a = 1325.7(2)pm, b = 1663.1(3) pm, c = 1925.2(3)pm, α = 95.869(14)°, β = 103.091(12)°, γ = 112.871(10)°).
    Notes: Bei der Umsetzung der Selenolato-Wolfram-Komplexe cp(CO)3WSeR; R = CH2Ph, CH2SiMe3, mit den ungesättigten Komplexfragmenten M(CO)5(THF); M = Cr, W, bzw. den Komplexkationen Ph3PAu+ und cp′(CO)2Fe+; cp′ = C5H5, C5Me5, entstehen zweikernige Komplexe, in denen das Selenatom eine positive Ladung bzw. Partialladung trägt. Dabei konnten folgende Verbindungen charakterisiert werden: [cp(CO)3W(μ-SeCH2Ph)Cr(CO)5] (1), [cp(CO)3W(μ-SeCH2Ph)W(CO)5] (2), [cP(CO)3W(μ-p C6H4{CH2SeCr(CO)5}2)W(CO) 3cp] (3), [cp(CO)3W(μ-SeCH2Ph)Fe(CO)2cp]+ClO 4-, (4), [cp(CO)3W(μ-SeCH2Ph)Fe(CO)2cp*]+ClO4-, (5) [cp(CO)3W(μ-SeCH2Ph)AuPPh3]+SbF6- (6), [cp(CO)3W(μ-SeCH2Ph)AuPPh3]+ClO4- (7) und [cp(CO)3W(μ-SeCH2SiMe3)AuPPh3]+SbF6- (8). Die Strukturen der Verbindungen 1, 2, 4 und 8 konnten durch Einkristall-Röntgenstrukturanalyse aufgeklärt werden (1: Raumgruppe P212121 (Nr. 19), Z = 16, a = 1744,5(3) pm, b = 2079,5(3) pm, c = 2435.7(5) pm; 2: Raumgruppe P1 (Nr. 2), Z = 8, a = 1318,94(14) pm, b = 1732,5(2) pm, c = 2119,9(2) pm, α = 89,805(10)°, β = 86,586(10)°, γ = 68,731(10)°; 4: Raumgruppe P1 (Nr. 2), Z = 2, a = 828,0(5) pm, b = 1027,4(5) pm, c = 1510,8(9) pm, α = 109,84(3)°, β = 99,45(4)°, γ = 91,43(3)°; 8: Raumgruppe P1 (Nr. 2), Z = 4, a = 1325,7(2) pm, b = 1663,1(3) pm, c = 1925,2(3) pm, α = 95,869(14)°, β = 103,091(12)°, γ = 112,871(10)°).
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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