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  • 1
    ISSN: 0044-2313
    Keywords: Metallodiphosphenes ; alkyl isocyanides ; 1,3-diphosphapropene ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal-substituted Diphosphenes. 37. Cleavage of the P=P Bond in the Metallodiphosphene (η5-C5Me5)(CO)2Fe—P=P—Mes* (Mes* = 2,4,6-tBu3C6H2) by Alkyl Isocyanides. Structure of (μ5-C5Me5)(CO)2Fe—P(NH—CH2C6H5)—C(NH—CH2C6H5)=PMes*The reaction of the metallodiphosphene (η5-C5Me5) · (CO)2Fe—P=P—Mes* (1) with two equivalents of cyclohexylisocyanide (3 a) or benzylisocyanide, respectively, afforded (E/Z)-mixtures of the 2,4-diimino-1,3-diphosphetanes (η5-C5Me5)(CO)2Fe—=NR (3 a: R = c-C6H11; 3 b: R = CH2C6H5). Complex 1 reacted with one equivalent of benzylisocyanide in an excess of benzylamine to give the 3-metallo-1,3-diphosphapropene (η5-C5Me5)(CO)2Fe—P·(NH—CH2C6H5)—C(NH—CH2C6H5)=PMes* (4). Constitution and configuration of the compounds 3 a, b, 4 were established by elemental analysis and spectra (IR, 1H-, 13C-, 31P-NMR, MS). The molecular structure of 4 was determined by x-ray diffraction analysis.
    Notes: Die Reaktion des Metallodiphosphens (η5-C5Me5)(CO)2Fe—P=P—Mes* (1) mit zwei Äquivalenten Cyclohexylisocyanid (2 a) bzw. Benzylisocyanid (2 b) liefert (E/Z)-Gemische der 2,4-Diimino-1,3-diphosphetane (η5-C5Me5)(CO)2Fe—=NR (3 a: R = c-C6H11; 3 b: R = CH2C5H5). Komplex 1 reagiert mit einem Äquivalent Benzylisocyanid in Benzylamin als Lösungsmittel zu dem 3-Metallo-1,3-diphosphapropen (η5-C5Me5)(CO)2Fe—P · (NHCH2C6H5)—C(NHCH2C6H5)=PMes* (4). Konstitution und Konfiguration der Verbindungen 3 a, b, 4 wurden durch Elementaranalysen und Spektren (IR, 1H, 13C, 31P-NMR, MS) ermittelt. Von 4 wurde zusätzlich eine Einkristall-Röntgenstrukturanalyse durchgeführt.
    Additional Material: 1 Ill.
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  • 2
    ISSN: 0044-2313
    Keywords: 1,2-Diphosphaferrocenes ; Transition Metal Complexes ; X-Ray Structure Analysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1,2-Diphosphaferrocenes as Ligands in Transition Metal Complexes. X-Ray Structure Analysis of [(η5-1,3-tBu2C5H3){η5-1,2-[Co2(CO)6]-3,4-(Me3SiO)2-5-(Me3Si)P2C3}]Reaction of metallo-1,2-diphosphapropene (η5-tBuC5H4)(CO)2Fe—P(SiMe3)—P=C(SiMe3)2 with (Z-cyclooctene)Cr(CO)5 afforded the pentacarbonylchromium adduct of a 1,2-diphosphaferrocene [(η5-tBuC5C5H4){η5-1-[Cr(CO)5]-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] (1 c). Diphosphaferrocene [(η5-tBuC5H4){η5-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] (2 c) was formed when (η5-tBuC5H4)(CO)2FeBr was treated with (Me3Si)2P—P=C(SiMe3)2 in toluene at 60°C. Photolysis of molybdenum- and tungsten hexacarbonyl in the presence of [(η5-1,3-tBu2C5H3){η5-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] (2 b) gave the pentacarbonylmetal adducts 8 (M = Mo) and 9 (M = W), respectively. A corresponding manganese derivative resulted from the photochemical reaction of 2 b and (MeC5H4)Mn(CO)3. Treatment of 2 b with Co2(CO)8 yielded trinuclear [(η5-1,3-tBu2C5H3){η5-1,2-[Co2(CO)6]-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] (11). Constitution and configuration of compounds 1 c, 2 c, 8 - 11 were determined by elemental analyses and spectra (IR, 1H-, 13C-, 31P-NMR, MS). In addition the molecular structure of 11 was established by single crystal X-ray analysis.
    Notes: Die Reaktion des Metallo-1,2-diphosphapropens (η5-tBuC5H4)(CO)2Fe—P(SiMe3)—P=C(SiMe3)2 mit (Cycloocten)Cr(CO)5 liefert das Pentacarbonylchrom-Addukt eines 1,2-Diphosphaferrocenes [(η5-tBuC5H4){η5-1-[Cr(CO)5]-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] (1c). Das Carbonyl-metall-freie 1,2-Diphosphaferrocen [(η5-tBuC5H4){η5-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] (2 c) entsteht bei der Umsetzung von (η5-tBuC5H4)(CO)2FeBr mit (Me3Si)2P—P = C(SiMe3)2 in Toluol bei 60°C. Das 1,2-Diphosphaferrocen [(η5-1,3-tBu2C5H3){η5-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] (2 b) reagiert mit den Hexacarbonylen von Molybdän und Wolfram bei Bestrahlung zu den Pentacarbonylmetall-Addukten 8 (M = Mo) und 9 (M = W). Ein entsprechender Mangankomplex 10 wird bei der photochemischen Reaktion von 2 b mit (MeC5H4)Mn(CO)3 gebildet. Im Gegensatz hierzu entsteht bei der Behandlung von 2 b mit Co2(CO)8 der dreikernige Komplex [(η5-1,3-tBu2C5H3){η5-1,2-[Co2(CO)6]-3,4-(Me3SiO)2-5-(Me3Si)P2C3} Fe] (11). Konstitution und Konfiguration der Verbindungen 1 c, 2 c, und 8 - 11 wurden durch Elementaranalysen und Spektren (IR, 1H-, 13C-, 31P-NMR, MS) ermittelt. Von 11 wurde zusätzlich eine Einkristall-Röntgenstrukturanalyse durchgeführt.
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