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  • Inorganic Chemistry  (4)
  • 1970-1974  (4)
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  • 1
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Carbene Complexes, LIV. Synthesis of Transition Metal Carbonyl Ylide Complexes from Transition Metal Carbonyl Carbene ComplexesSecondary und tertiary alkylphosphines PX3 [X3 = (CH3)3, (C2H5)3, (n-C4H9)3, (CH3)2H] react with (alkoxycarbene)- or (alkylthiocarbene)pentacarbonyl complexes of chromium(0) and tungsten(0),(CO)5Cr[C(OCH3)C6H5], (CO)5W[C(OCH3)CH3] and (CO)5W[C(SCH3)CH3], at low temperatures to give the corresponding ylidepentacarbonylmetal complexes (CO)5M[C(PX3)(YCH3)(Z)] (M = Cr, W; Y = O, S; Z = CH3, C6H5) under addition of the phosphines to the carbene carbon atom. The structures of the pale yellow, diamagnetic, and partially very thermolabile compounds were established by analysis, i.r., n.m.r., and mass spectra. The partial thermal conversion of (CO)5Cr[C(P(CH3)2H)(OCH3)(C6H5)] in acetone was shown to yield (CO)5Cr{P(CH3)2[CH(OCH3)(C6H5)]}.
    Notes: Durch Umsetzung sekundärer und tertiärer Alkylphosphine PX3 [X3 = (CH3)3, (C2H5)3, (n-C4H9)3, (CH3)2H] mit den (Alkoxycarben)- bzw. (Alkylthiocarben)pentacarbonyl-Komplexen von Chrom(0) und Wolfram(0), (CO)5Cr[C(OCH3)C6H5], (CO)5W[C(OCH3)CH3] und (CO)5W[C(SCH3)CH3], bei tiefen Temperaturen wurden unter Addition der Phosphine an das Carbenkohlenstoffatom entsprechende Ylid-pentacarbonylmetall-Komplexe (CO)5 M[C(PX3) (YCH3)(Z)] (M = Cr, W; Y = O, S; Z = CH3, C6H5) erhalten. Die Strukturen der schwach gelblichen, diamagnetischen, z T. sehr thermolabilen Verbindungen wurden durch Analyse, IR-, NMR- und Massenspektren gesichert. Die partielle thermische Reaktion von (CO)5Cr[C(P(CH3)2H)(OCH3)(C6H5)] in Aceton zu (CO)5Cr{P(CH3)2[CH(OCH3)(C6H5)]} wurde nachgewiesen.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Carbene Complexes, LXIX. Isomerism of cis- and trans-(Alkoxycarbene)tetracarbonyl(phosphine)metal Complexes and Dependence of the Equilibrium ConstantsSolutions of cis- and trans-(alkoxycarbene)tetracarbonyl(phosphine)metal complexes, (CO)4M(PR3)[COR′)R″] [M=Cr, W; R3=(CH3)3, (C2H5)3, (n-C4H9)3, (n-C8H17)3, (i-C2H7)3, (C6H11)3, (C2H5)2C6H5, (C6H5)2C2H5, (C6H5)3, (p-C6H4CH3)3, (p-C6H4F)3, (m-C6H4F)3; R′=CH3, C2H5; R″=CH3, C2H5, i-C3H7, C6H7, C6H5] on heating isomerize to an equilibrium situation. The equilibrium constants are dependent upon the solvent, the central metal, the phosphine group and the carbene ligand.
    Notes: cis-u. trans-(Alkoxycarben)tetracarbonyl(phosphin)metall-Komplexe, (CO)4M(PR3)[(OR′)R′] [M=Cr, W; R3=(CH3)3, (C2H5)3, (n-C4H9)3, (n-C8H11)3, (C3H5)3, (C 6H11)3, (C2H5)2C6H5, (C2H5)2C2H5, (C6H5)3, (p-C6H4CH3)3, (p-C6H4F)3, (m-C 6H4F)3; R′=CH3, C2H5; R′=CH3, C2H5, i-C3H7, C6H5] isoerisieren beim Erwärmen in Lösung bis zu einem Gleichgewichtszustand. Die lage dieses Isomerisierungsgleichgewichts ist durch die Wahl des Lösungsmittels. des Zentralmetalls der Phosphingruppe und des Carbenliganden beeinflußbar.
    Additional Material: 6 Tab.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 2459-2467 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Carbene Complexes, LXXIV. Reversible Addition of Tertiary Phosphines on Pentacarbonyl(methoxymethylcarbene) Metal ComplexesThe reaction of tertiary phosphines PR3 [PR3 = P(C4H9)3, P(C2H5)2C6H5, P(i-C3H7)3] with pentacarbonyl(methoxymethylcarbene)metal complexes of chromium(O) and tungsten(O), (CO)5Cr[C(OCH3)] and (CO)5W[C(OCH3)], at low temperatures results in a reversible addition of the phosphine to the carbene ligand. The addition-dissociation-equilibrium constants depend on the temperature, the solvent, the phosphine, and the central metal.
    Notes: Bei der Umsetzung von tertiären phosphinen PR3 [PR3 = P(C4H9)3. P(C2H5)2 C6H5. P(i-C3H7)3] mit Pentacarbonyl(methoxymethylcarben)chrom(O) bzw. -wolfram(O). (CO)5Cr[C(OCH3)CH3] bzw. (CO)5W[C(OCH3)CH3], bei tiefen Temperaturen erfolgt eine Gleichgewichtskonstanten hängen von der Temperatur, dem Lösungsmittel, der Art des Phosphins und des Zentralmetalls ab.
    Additional Material: 5 Tab.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 107 (1974), S. 657-672 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Carbene Complexes, LXVIII. Synthesis of cis- and trans-Tetracarbonyl(carbene)(phosphine) Complexes of Chromium(0) and Tungsten(0)Thermal reaction in the range 60 to 80°C and photochemical reaction at room temperature of tertiary phosphines PX3 [X3=(CH3)3, (C2H5)3, (n-C8H17)3, (i-c3H7)3, (C6H11)3, (C2H5)2C6H5, (C6H5)2 C2H5, (C6H5)3, (p-C6H4CH3)3, (p-C6H4F)3, (m-C6H4F)3] with pentacarbony(carbene) complexes of chromium (0) and tungsten (0), (CO)5Cr[C(R′)R″] and (CO)4M(PR3)[C(R′)R″] and trans-(CO)4M(PR3)[C(R′)R″]. Photochemical reaction at low temperatures and in the case where R′==NH2 and NHCH3, yields only the cis-isomers. The structures of the yellow to red, diamagnetic compounds were established by analyses and spectra.
    Notes: Bei der thermischen Umsetzung von tertiären Phosphinen PX3 [X3=(CH3)3, (C2H5)3, (n-C4H9)3, (n-C8H17)3, (C3H7)3, (C6H11)2C6H5, (C6H5)2C2H5)3, (p-C6H4CH3)3- (p-C6H4F)3, (m-C 6H4F)3] mit Pentacarbonyl(carben)-Komplexen von Chrom (0) und Wolfram(0), (CO)5Cr[(R′)R″] und (CO)5W[ C(R′)R″] (R′=OCH3, OC2H5; R″==CH3, C2H5, i-C3H7, C6H5), erhält man im Temperaturbereich zwischen 60 und 80°C unter CO-Abspaltung sowohl die cis-als auch die trans-Isomeren der Tetracarbonyl(carben)-(phosphin)-Komplexe (CO)4M(PR3)[C(R′)R″]. desgleichen bei photochemischer Reaktion bei Raumtemperatur. Bei photochemischer Umsetzung bei tiefen Temperaturen und für R′=NH2 oder NHCH3 fallen jedoch nur die cis-Verbindungen an. Die Konstitutionen der gelben bis roten, diamagnetischen Verbindungen wurden analytisch und spektroskopisch gesichert.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
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