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  • 1975-1979  (4)
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 108 (1975), S. 163-173 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Complex Chemistry of Four Center π Systems, IX. 2,2′Bipyridyl- a „Bad Ligand“ for Metals in Low Oxidation StatesThe comparison of the complex series LMo(CO)4, LMo(CO)3PBu3, and LMo(CO)2(PBu3)2 [L = t-C4H9—N=CH—CH=N—t-C4H9 (DAB), 2,2′-bipyridyl (bpy)] and their paramagnetic monoanions reveals that the π-acceptor quality of bpy is only about one half of that of DAB. This follows from EPR spin densities at the coordination sites and 31P coupling constants as well as from the solvatochromism of the absorption in the electronic spectra. π-Interaction (β) is for bpy approximately 0.6 eV, while it reaches 1 eV for DAB.
    Notes: Der Vergleich der Komplexreihen LMo(CO)4, LMo(CO)3PBu3 und LMo(CO)2(PBu3)2 [L = t-C4H9—N=CH—CH=N—t-C4H9 (DAB); 2,2′-Bipyridyl (bpy)] und ihrer paramagnetischen Monoanionen zeigt, daß die π-Akzeptorfähigkeit von bpy nur etwa halb so groß ist wie die von DAB. Das ergibt sich aus den Spindichten an den Koordinationszentren und den 31P-Kopplungen im ESR sowie aus der Solvatochromie der Absorptionen in den Elektronenspektren. Die π-Wechselwirkung (β) erreicht für bpy nur ca. 0.6 eV, für DAB 1 eV.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 108 (1975), S. 3025-3029 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Intramolecular cis-trans Exchange of Carbonyl Ligands in (L—L)M(CO)4 ComplexesTetracarbonyl complexes of VIb-metals with glyoxal bis(arylimines) as bidentate ligands show cis/trans exchange of the carbonyl ligands as found by means of the 13C n.m.r. spectrum. The i.r. data indicate a distorded octahedron in the ground state and the 13C n.m.r. spectrum a trigonalprismatic transition state. The activation barrier has been determined in 13CO-enriched compounds.
    Notes: Tetracarbonylkomplexe der VIb-Metalle mit Glyoxal-bis(aryliminen) als Chelatliganden zeigen im 13C-NMR-Spektrum cis/trans-Austausch der Carbonylliganden. Auf Grund des IR-Spektrums wird auf ein verzerrtes Oktaeder als Grundzustand und mit Hilfe des 13C-NMR-Spektrums auf einen trigonal-prismatischen Übergangszustand geschlossen. Die Aktivierungsbarrieren wurden an 13CO-angereicherten Komplexen bestimmt.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1657-1664 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metalation of a Non-activated Alkyl Group in Nickel ComplexesThe diazadiene (DAD)glyoxalbis(diisopropylmethylimine) (1) reacts with anhydrous nickel bromide to yield (DAD)NiBr2 (2). Its reactions with main group metal alkyls lead to rather unstable intermediates. With the bulky O-tolylmagnesium bromide -under formal HBr abstraction- metalation of the diisopropylmethyl substituent occurs in γ-position to the next activating center (N) with formation of an N—C chelate. Properties and structure of this product 3 from this novel alkane activation reaction are discussed.
    Notes: Aus dem Diazadien (DAD) Glyoxalbis (diisopropylmethylimin) (1) und wasserfreiem Nickelbromid wird (DAD)NiBr2 (2) erhalten, dessen Reaktion mit Hauptgruppenmetall-alkylen zu wenig stabilen Zwischenprodukten führt. Mit dem sperrigen O-Tolylmagnesiumbromid wird unter formaler HBr-Abspaltung die Metallierung des Diisopropylmethyl-Rests von 2 in γ-Stellung zum nächsten aktivierenden Zentrum (N) unter Bildung eines N—C-Chelatrings erreicht. Eigenschaften und Struktur dieses Produkts (3) einer neuartigen Alkanaktivierung werden diskutiert.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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