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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 499-504 
    ISSN: 1434-1948
    Keywords: Alkynes ; Heterocycles ; Cyclizations ; Cobalt ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The following monocyclic and bicyclic 14-membered diynes were treated with [CpCo(cod)]: 1-oxacyclotetradeca-4,11-diyne (2), 1,8-dioxacyclotetradeca-4,11-diyne (3), cyclotetradeca-4,11-diynone (4), cyclotetradeca-4,11-diyne-1,8-dione (5), 1,1,8,8-tetramethyl-1,8-disilacyclotetradeca-4,11-diyne (6), 1-allyl-1-azacyclotetradeca-4,11diyne (7), 1,8-dipropyl-1,8-diazacyclotetradeca-1,11-diyne (8), 1,8-diallyl-1,8-diazacyclotetradeca-4,11-diyne (9), 1,8-diazabicyclo[6.6.4]octadeca-4,11-diyne (10), 1,8-diazabicyclo[6.6.6]eicosa-4,11-diyne (11), 1,10-diazabicyclo[8.6.6]docosa-13,19-diyne (12) and 1,12-diazabicyclo[10.6.6]tetracosa-15,21-diyne (13). In all cases we obtained an intramolecular cyclobutadiene complex stabilized with a CpCo fragment (15-26). For 3 we could isolate, besides the cyclobutadiene complex 16, the trimerization product 28. In the cases of 15, 16, 18, 20, 23, 25, and 26 the structure of the cylobutadiene complexes could be confirmed by X-ray studies. Common to all structures is a boat-like conformation of the tricyclic unit containing the cyclobutadiene ring. The two cycloheptene units adopt a chair conformation in which the heteroatom is removed from the metal center.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 1303-1310 
    ISSN: 1434-193X
    Keywords: Ketones ; Alkynes ; Cyclic voltammetry ; Photoelectron spectroscopy ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The fourteen-membered ring of 7,7,12,12-tetramethyl-1,4-dioxacyclotetradecane-8,9,10,11-tetrone (4) was built up from 1,2-bis(2′-chloroethoxy)ethane, two units derived from isobutyric acid and acetylene. Key intermediates were 2,2,11,11-tetramethyl-5,8-dioxadodecane-1,12-diol (8), 7,7,12,12-tetramethyl-1,4-dioxa-9-cyclotetradecyne-2,8-diolprotected by one tetrahydropyran group (15), and 8,11-dihydroxy-7,7,12,12-tetramethyl-1,4-dioxacyclotetradecane-9,10-dione (18). X-ray investigation on single crystals of the (R,S) isomer 18a revealed a transannular interaction between the dioxaethane bridge and the dicarbonyl moiety. Calculations (HF/6-31G*) on 4 predict relatively short distances between the oxygen atoms of the dioxyethane bridge and the (CO)4 part. Investigations by means of cyclic voltammetry, PE and UV/Vis spectroscopy on 4 reveal an interaction between the dioxaethane bridge and the (CO)4 group.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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