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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: Preparation and Properties of, and Reactions with, Metal-Containing Heterocycles, XXIV. P- and S-isomeric Heteronickelacyclopentadienes as Trapping Products of the Unstable Three-membered Ring Systemswith Activated AlkynesThe unstable three-membered ring systems (2a, b) (L = h5-C5H5), which dimerize immediately at room temperature to give [LNiS=PR21]2 (3a, b), are obtained by reaction of L2Ni with diorganylphosphane sulfides R21HPS (1a, b). Between 2a, b and 3a, b there exists a dissociative equilibrium. 2a, b, however, are trapped with activated alkynes of the type R2C ≡ CR2 with formation of the S- and P-isomeric heteronickelacyclopentadienes (4aS - dS) and (4bP - dP) which can be differentiated by their colour and for R1=CH3 also with respect to the 1H NMR spectra. According to an X-ray structural analysis, 4aS crystallizes in the monoclinic space group P21/n with Z = 4.
    Notes: Bei der Umsetzung von L2Ni (L = h5-C5H5) mit den Diorganylphosphansulfiden R21HPS (1a, b) erhält man die instabilen, dreigliedrigen Ringsysteme (2a, b), die bei Raumtemperatur sofort zu [LNiS=PR21]2 (3a, b) dimerisieren. Zwischen 2a, b und 3a, b liegt ein dissoziatives Gleichgewicht vor. 2a, b lassen sich jedoch mit aktivierten Alkinen R2C ≡ CR2 unter Bildung der S- und P-isomeren Heteronickelacyclopentadiene (4aS - dS) und (4bP - dP) abfangen, welche sich in ihrer Farbe und für R1=CH3 auch in den 1H-NMR-Spektren unterscheiden. Nach einer Röntgenstrukturanalyse kristallisiert 4aS in der monoklinen Raumgruppe P21/n mit Z = 4.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
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