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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1623-1629 
    ISSN: 1434-1948
    Keywords: (1-Alkynyl)carbene complexes ; Pyrroles ; Imines ; Mesoionic compounds ; Tungsten complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of the [(1-alkynyl)carbene]tungsten complex (CO)5W=C(OEt)C≡CPh (1a) with non-enolizable imines, e.g. 9-fluorenone imines 2 [NR = N(iPr), N(c-C6H11)], affords novel mesoionic pyrrolium carbonyltungstates 3 (by [3+2] cycloaddition) together with dihydropyrroles 4 (by dichotomy of the C=N bond and subsequent insertion of the carbene carbon atom into an NC-H bond). Cross-conjugated azametallatrienes 6 and pentacarbonyltungsten complexes 7 of the dihydropyrroles 4 have been identified to be precursors to compound 4. Compounds 3b, 4a, and 6a have been characterized by X-ray crystal structure analyses.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1079-1084 
    ISSN: 0009-2940
    Keywords: Cyclopropenylium compounds ; Methylenecyclopropenes ; Isonitrile insertion ; Methylenecyclobutenone imine derivatives ; Cyclopropenylioborate betaines ; C-C coupling ; Zirconium ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis(propynyl)zirconocene was treated with B(C6F.5)3 and then with two equivalents of tert-butyl isocyanide to yield the organometallic three-membered ring product 8. Subsequent hydrolysis gives the substituted (2-iminioethylidene)cyclopropeneborate betaine system 9 that exhibits a pronounced cyclopropenylioborate betaine character. This follows from its characteristic structural features (X-ray crystal-structure analysis of the isomer cis-9) and its chemical features. Complex 9 undergoes a very facile cis/trans isomerization by formal rotation around the exocyclic partial CC-double bond (ΔG+ ≈ 17 kcal mol-1). Compound 9 reacts cleanly in methanol solution with tert-butyl isocyanide by insertion and ring enlargement to form the four-membered ring system 12. Compound 12 was also characterized by X-ray diffraction.
    Type of Medium: Electronic Resource
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