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  • 1
    Electronic Resource
    Electronic Resource
    The First Titanacyclic Five-Membered Cumulene. Synthesis, Structure, and Reactivity (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 967-971 
    Details
    ISSN: 0009-2940
    Keywords: Titanocene ; Diyne ; Cumulene ; Titanacyclopentadiene ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The first five-membered titanacyclic cumulene (5) was prepared by treatment of the titanocene generator Cp2Ti(Me3SiC2SiMe3) with the di-tert-butylbutadiyne in a molecular one-to-one ratio. The reaction of 5 with “Cp2Zr” or of the analogous complex with “Cp2Ti” leads to cleavage of the central C-C bond in the metallacyclocumulene complexes to afford the same product, the heterodimetallic ρ, π,-alkynyl-bridged titanocene-zirconocene complex Cp2Zr(μ-η1η2-C≡CtBu)Cp2Ti(μ-η1η2-C≡CtBu) (6), in which each alkynyl group is π-bonded to one and π-bonded to the other metal as shown by X-ray diffraction studies. In solution the two alkynyl groups become equivalent. The coupling reaction of “Cp2Ti” with bis(trimethylsilyl)butadiyne in a one-to-two molecular ratio leads to the unsymmetrically substituted titanacyclopentadiene (7).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951281002
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  • 2
    Electronic Resource
    Electronic Resource
    Ring-Enlargement and Ring-Opening Reactions of Benzoxazole, Thiazoles, and Benzisoxazole by Zirconocene-Alkyne Complexes (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 207-211 
    Details
    ISSN: 0009-2940
    Keywords: Zirconocene ; Titanocene ; Benzoxazoles ; Thiazoles ; Benzisoxazoles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Zirconocene alkyne complexes Cp2Zr(L)(Me3SiC2R) (L = Py, THF; R = SiMe3 tBu) react with heterocyclic compounds like benzoxazole and related thiazoles to yield ring-expanded adducts (1-3) and (4, 5) by formal C-X (X = O, S) bond cleavage and coupling with the coordinated alkyne. In the case of benziso-xazole, the alkyne is not coupled but eliminated, and with ring-enlargement of the benzisoxazole a N-bridged dimer (6) is formed. The obtained complexes 1, 3, and 6 were characterized by NMR spectra and crystal structure analysis.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961290214
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