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  • 1
    ISSN: 0044-2313
    Keywords: Chromium ; Palladium ; Copper Phosphaneimine Complexes ; Syntheses ; IR Spectra ; Crystal Structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Silylated Phosphaneimine Complexes of Chromium(II), Palladium(II), and Copper(II). The Crystal Structures of [CrCl2(Me3SiNPMe3)2], [PdCl2(Me3SiNPEt3)2], and [CuCl2(Me3SiNPMe3)]2The title compounds have been prepared by the reaction of the silylated phosphaneimines Me3SiNPR3 (R = CH3, C2H5) with CrCl2(THF)2, PdCl2 and CuCl2, respectively, in dichloromethane suspensions. All donor-acceptor complexes were characterized by IR spectroscopy and by crystal structure determinations.[CrCl2(Me3SiNPMe3)2]: Space group Pccn, Z = 4, structure determination with 2104 observed unique reflections, R = 0.045. Lattice dimensions at -70°C: a = 1326.3, b = 1562.5, c = 1171.5 pm. Within the monomeric molecular structure the chromium atom is planarly coordinated within the trans-configuration of the Cl atoms and the N atoms with distances of Cr—Cl = 235.94 pm and Cr—N = 211.7 pm.[PdCl2(Me3SiNPEt3)2]: Space group P21/n, Z = 2, structure determination with 2412 observed unique reflections, R = 0.031. Lattice dimensions at 20°C: a = 917.3, b = 1390.2, c = 1161.7 pm, β = 95.80°. Within the monomeric molecular structure the palladium atom is planarly coordinated within the trans-configuration of the Cl atoms and the N atoms with distances of Pd—Cl = 222.9 pm and Pd—N = 209.5 pm.[CuCl2(Me3SiNPMe3)2]: Space group Pbca, Z = 4, structure determination with 1861 observed unique reflections, R = 0.067. Lattice dimensions at -70°C: a = 1440.2, b = 1205.1, c = 1536.5 pm. The compound forms centrosymmetric dimeric molecules, in which the Cu atoms are linked via almost symmetrical chloro-bridges with Cu—Cl distances of 231.4 pm. The distance Cu—N is 196.7 pm.
    Notes: Die Titelverbindungen entstehen bei der Einwirkung der silylierten Phosphanimine Me3SiNPR3 (R = CH3, C2H5) auf CrCl2(THF)2, PdCl2 und CuCl2 in Dichlormethan-Suspension. Die drei Donor-Acceptor-Komplexe werden durch ihre IR-Spektren und durch Kristallstrukturanalysen charakterisiert.[CrCl2(Me3SiNPMe3)2]: Raumgruppe Pccn, Z = 4, Strukturlösung mit 2104 unabhängigen beobachteten Reflexen, R = 0,045. Gitterkonstanten bei -70°C: a = 1326,3; b = 1562,5; c = 1171,5 pm. In der monomeren Molekülstruktur ist das Chromatom planar in der trans-Konfiguration von den Cl-Atomen und den N-Atomen der Phosphanimin-Liganden koordiniert mit Abständen Cr—Cl = 235,94 pm und Cr—N = 211,7 pm.[PdCl2(Me3SiNPEt3)2]: Raumgruppe P21/n, Z = 2, Strukturlösung mit 2412 unabhängigen beobachteten Reflexen, R = 0,031. Gitterkonstanten bei 20°C: a = 917,3; b = 1390,2; c = 1161,7 pm, β = 95,80°. In der monomeren Molekülstruktur ist das Palladiumatom planar in der trans-Konfiguration von den Cl-Atomen und den N-Atomen der Phosphaniminliganden koordiniert mit Abständen Pd—Cl = 222,9 pm und Pd—N = 209,5 pm.[CuCl2(Me3SiNPMe3)]2: Raumgruppe Pbca, Z = 4, Strukturlösung mit 1861 unabhängigen beobachteten Reflexen, R = 0,067. Gitterkonstanten bei -70°C: a = 1440,2; b = 1205,1; c = 1536,5 pm. Die Verbindung bildet zentrosymmetrische dimere Moleküle, in denen die Cu-Atome über nahezu symmetrische Chlorobrücken mit Cu—Cl-Abständen von 231,4 pm verknüpft sind. Der Abstand Cu—N beträgt 196,7 pm.
    Additional Material: 3 Ill.
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  • 2
    ISSN: 0044-2313
    Keywords: The hydrogenation of Si-chlorinated, C-spiro-linked 2,4-disilacyclobutanes with LiAlH4 and iBu2AlH ; Access to (H3Si)2CH—SiH2—CH(SiH3)—SiH2—CH(SiH3)2 and Si8C3H20 ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Formation of Organosilicon Compounds. 111. The Hydrogenation of Si-chlorinated, C-spiro-linked 2,4-Disilacyclobutanes with LiAlH4 or iBu2AlH. The Access to Si8C3H20The hydrogenation of Si-chlorinated, C-spiro-linked 2,4-disilacyclobutanes containing C(SiCl3)2 terminal groups with LiAlH4 in Et2O proceeds under complete cleavage of the fourmembered rings and under elimination of one SiH3 group. Such, Si8C3Cl20 4 forms (H3Si)2CH—SiH2—CH(SiH3)—SiH2—CH(SiH3)2 4α, and even Si8C3H20 4a with LiAlH4 forms 4α. The hydrogenation of related compounds containing however CH(SiCl3) terminal groups similarly proceeds under ring cleavage but no SiH3 groups are eliminated. Such, (Cl3Si)CH(SiCl2)2CH(SiCl3) 41 forms (H3Si)2CH—SiH2—CH2(SiH3) 41α. However, in reactions with iBu2AlH in pentane neither the disilacyclobutane rings are cleaved nor are SiH3 groups eliminated. Only by this method Si8C3H20 is accessible from 4, Si6C2H16 3a from Si6C2Cl16 3 and Si4C2H12 41a from 41. C(SiCl3)4 cleanly produces C(SiH3)4.Based on the knowledge about the different properties of LiAlH4 and iBu2AlH in hydrogenation reactions of disilacyclo-butanes it was possible to elucidate the composition and the structures of the hydrogenated derivatives of the product mixture from the reaction of MeCl2Si—CCl2—SiCl3 with Si(Cu) [1] and to trace them back to the initially formed Si chlorinated disilacyclobutanes Si6C2Cl15Me 34, Si6C2Cl14Me2 35, Si8C3Cl19Me 36 and Si8C3Cl18Me2 37.Compound 4a forms colourless crystals of space group P1 with a = 799.7(6), b = 1263.6(12), c = 1758.7(14) pm, α = 103.33(7)°, β = 95.28(6)°, γ = 105.57(7)° and Z = 4.
    Notes: Si-chlorierte, C-spiroverbrückte 2,4-Disilacyclobutane mit C(SiCl3)2-Endgruppen, wie Si8C3Cl20 4, reagieren mit LiAlH4 in Et2O unter Spaltung der Vierringe und Abspaltung einer SiH3-Gruppe. So bildet 4 (H3Si)2CH—SiH2—CH(SiH3)—SiH2—CH(SiH3)2 4α. Ebenso reagiert Si8C3H20 4a zu 4α. (Cl3Si)CH(SiCl2)2CH(SiCl3) 41 (CHSiCl3-Endgruppen) reagiert unter Ringspaltung, aber ohne Abspaltung einer SiH3-Gruppe zu (H3Si)2CH—SiH2—CH2(SiH3) 41α. Dagegen erfolgen die Umsetzungen mit iBu2AlH in Pentan unter Erhalt der Ringgerüste und ohne Abspaltung einer SiH3-Gruppe. So bildet 4 das Si8C3H20 4a, 3 das Si6C2H16 3a, 41 das Si4C2H12 41a und C(SiCl3)4 das C(SiH3)4.Mit diesen Kenntnissen über die unterschiedlichen Eigenschaften von LiAlH4 und iBu2AlH bei der Hydrierung von Disilacyclobutanen war es möglich, die Zusammensetzung und die Strukturen der hydrierten Derivate aus dem Produktgemisch der Reaktion von MeCl2Si—CCl2—SiCl3 mit Si(Cu) [1] aufzuklären und auf die ursprünglich gebildeten Si-chlorierten Disilacyclobutane Si6C2Cl15Me 34, Si6C2Cl14Me2 35, Si8C3Cl19Me 36 und Si8C3Cl18Me2 37 zurückzuführen. 4a bildet farblose Kristalle und kristallisiert in der Raumgruppe P1; a = 799,7(6), b = 1263,6(12), c = 1758,7(14) pm, α = 103,33(7)°, β = 95,28(6)°, γ = 105,57(7)° mit Z = 4.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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