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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 622 (1996), S. 867-872 
    ISSN: 0044-2313
    Keywords: Phosphoraneiminato Complexes ; Cobalt ; Zinc ; Crystal Structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Phosphoraneiminato Complexes of Cobalt and Zinc with Heterocubane Structure. Crystal Structures of [CoI(NPMe3)]4 and [ZnI(NPMe3)]4The title compounds have been prepared from CoI2 and ZnI2, respectively, and Me3SiNPMe3 by fusion reactions at 180°C in the presence of sodium fluoride. They crystallize from dichloromethane as dark green (Co) or colourless (Zn) single crystals including three molecules CH2Cl2 per formula unit, which were characterized by crystal structure determinations. [CoI(NPMe3)]4 · 3 CH2Cl2: Space group P3m1, Z = 2, structure solution with 2376 independent reflections, R = 0.033. Lattice dimensions at -50°C: a = b = 1455.8, c = 1270.5 pm.[ZnI(NPMe3)]4 · 3 CH2Cl2: Space group P3m1, Z = 2, structure solution with 2197 independent reflections, R = 0.043. Lattice dimensions at -60°C: a = b = 1454.9, c = 1270.5 pm. Both complexes are isostructural with one another. They form heterocubane structures in which the metal atoms are linked via μ3-N-bridges of the phosphoraneiminato groups with M4N4 bridge-type bond angles close to 90°.
    Notes: Die Titelverbindungen werden durch Reaktionen von CoI2 bzw. ZnI2 mit dem silylierten Phosphanimin Me3SiNPMe3 durch Schmelzreaktion bei 180°C in Gegenwart von Natriumfluorid synthetisiert. Sie kristallisieren aus Dichlormethan als dunkelgrüne (Co) bzw. farblose (Zn) Einkristalle mit drei Molekülen Dichlormethan pro Formeleinheit, die wir durch Kristallstrukturanalysen charakterisiert haben. [CoI(NPMe3)]4 · 3 CH2Cl2: Raumgruppe P3m1, Z = 2, Strukturlösung mit 2376 unabhängigen Reflexen, R = 0,033. Gitterkonstanten bei -50°C: a = b = 1455,8; c = 1270,5 pm.[ZnI(NPMe3)]4 · 3 CH2Cl2: Raumgruppe P3m1, Z = 2, Strukturlösung mit 2197 unabhängigen Reflexen, R = 0,043. Gitterkonstanten bei -60°C: a = b = 1454,9; c = 1270,5 pm. Die beiden miteinander isotypen Verbindungen bilden Heterocuban-Strukturen, in denen die Metallatome über μ3-N-Brücken der Phosphaniminato-Gruppen verknüpft sind mit M4N4-Brückenbindungswinkeln nahe bei 90°.
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  • 2
    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.
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  • 3
    ISSN: 0044-2313
    Keywords: Phosphorane Iminato Complexes ; Copper(II) ; Synthesis ; Magnetic Behaviour ; EPR Spectrum ; Crystal Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: [Cu4(NPMe3)3(O2C—CH3)5] - a Tetrameric Phosphorane Iminato Complex of Copper(II). Synthesis, Crystal Structure, Magnetic Behaviour, and EPR SpectrumThe title compound and the corresponding benzoate complex [Cu4(NPMe3)3(O2C—C6H5)5] have been prepared by reactions of copper(II)acetate and copper(II)benzoate, respectively, with Me3SiNPMe3 in dichloromethane. Both complexes are characterized by IR spectroscopy. The acetate complex is additionally characterized by the measurement of the magnetic susceptibility, by its EPR spectrum, and by a crystal structure determination.[Cu4(NPMe3)3(O2C—CH3)5] · CH2Cl2: Space group I41/a, Z = 16, structure solution with 7 960 independent reflections, R = 0.044. Lattice dimensions at -70°C: a = b = 3 670.6; c = 1 091.9 pm. The structure consists of four Cu atoms which are arranged at the corners of a distorted tetrahedron with Cu…Cu distances between 290 and 318 pm. Three of the faces of the tetrahedron are linked by μ3-N atoms of the phosphorane iminato groups. Three of the acetate ligands form chelates, the other two are monofunctionally coordinated. Three of the copper atoms have a planar surrounding, the forth Cu atom has a (4 + 1) coordination.
    Notes: Die Titelverbindung sowie der entsprechende Benzoat-Komplex [Cu4(NPMe3)3(O2C—C6H5)5] wurden durch Reaktion von Kupfer(II)acetat bzw. von Kupfer(II)benzoat mit Me3SiNPMe3 in Dichlormethan hergestellt und durch ihre IR-Spektren charakterisiert. Der Acetatkomplex wurde zusätzlich durch die Messung der magnetischen Suszeptibilität, des EPR-Spektrums und durch eine Kristallstrukturanalyse charakterisiert.[Cu4(NPMe3)3(O2C—CH3)5] · CH2Cl2: Raumgruppe I41/a, Z = 16, Strukturlösung mit 7 960 unabhängigen Reflexen, R = 0,044. Gitterkonstanten bei -70°C: a = b = 3 670,6; c = 1 091,9 pm. Die Struktur besteht aus vier Cu-Atomen, die ein verzerrtes Tetraeder bilden mit Cu…Cu-Abständen zwischen 290 und 318 pm. Drei der Tetraederflächen sind durch μ3-N-Atome dreier NPMe3--Gruppen überbrückt, drei der Acetatliganden sind chelatartig gebunden, während zwei Acetatgruppen monofunktionell koordinieren. Drei der Cu-Atome haben planare Umgebung, das vierte hat eine (4 + 1)-Koordination.
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