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  • Wiley-Blackwell  (2)
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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 113 (1980), S. 586-597 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Isolation and Energy Well of the 2,3-Dimethylene-1,4-cyclohexadiyl DiradicalIrradiation of both 5,6-dimethylene-2,3-diazabicyclo[2.2.2]oct-2-ene (1) and 2,3-dimethylene-bicyclo[2.2.1]octan-7-one (2) matrix isolated in argon yields the 2,3-dimethylene-1,4-cyclohexadiyl diradical (8), which was characterized by its UV and IR spectra. From the decomposition rate of 1, the dimerisation rate of 8, determined by flash photolysis of 1, and the product ratio of the monomeric and dimeric products obtained from 8, the energy well of 8 has been determined to be 23.8 kcal mol-1.
    Notes: Die Bestrahlung von 5,6-Dimethylen-2,3-diazabicyclo[2.2.2]oct-2-en (1) sowie 2,3-Dimethylen-bicyclo[2.2.1]octan-7-on (2) in einer Argon-Matrix liefert das 2,3-Dimethylen-1,4-cyclohexadiyl-Diradikal (8), das durch sein UV- sowie sein IR-Spektrum charakterisiert wurde. Aus der Zerfallsgeschwindigkeit von 1, der durch Blitzlichtphotolyse von 1 ermittelten Dimerisierungs-geschwindigkeit von 8 und dem Verhältnis der sich von 8 ableitenden monomeren und dimeren Produkte wird für 8 eine Energiemulde von 23.8 kcal mol-1 bestimmt.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Low Temperature Matrix Photolysis of C — C and C — H Bonds in Tricarbonyl Complexes of 5,5-DialkylcyclopentadienesThe photochemical cleavage of C  -  C single bonds in tricarbonyl(η4-5,5-dialkylcyclopentadiene)-iron complexes 4 and 7 was investigated at 10 K in an argon matrix. In the two-step conversion CO is initially abstracted and η-alkyl(η5-cyclopentadienyl) systems 6 and 9 are formed via coordinatively unsaturated dicarbonyl species 5 and 8. Alkylmetal complexes containing bT-H-atoms (e.g. 11) are converted in a further photochemical reaction into hydride complexes (e. g. 10 and 12) via β-H elimination.
    Notes: Die photochemische Spaltung von C — C-Bindungen in den Tricarbonyl(η4-5,5-dialkyl-cyclopentadien)eisen-Komplexen 4 und 7 wurde bei 10 K in einer Argon-Matrix studiert. Bei der zweistufigen Umwandlung werden zunächst unter CO-Abspaltung die koordinativ ungesättigten Dicarbonyl-Komplexe 5 bzw. 8 gebildet. Danach entstehen die η-Alkyl(η-cyclopentadienyl)-Systeme 6 bzw. 9. Enthalten die gebildeten Alkylmetall-Komplexe (wie z. B. 11) β-H-Atome, so werden sie in einer weiteren photochemischen Reaktion unter β-H-Eliminierung in Hydrid-Komplexe (wie 10 und 12) umgewandelt.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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