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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 713-724 
    ISSN: 0009-2940
    Keywords: Bicyclo[3.2.0]hepta-1,3-dienyl complexes ; Calculations, semiempirical ; Alkyne trimerization ; Cobalt complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three isomeric bicyclo[3.2.0]heptadienes 1 - 3 are compared by semiempirical calculations. Experimental attempts directed to the synthesis of derivatives of 1 are described. The synthesis, properties and some reactions of (η51-bicyclo[3.2.0]hepta-1,3-dienyl)(η41-cycloocta-1,5-diene)cobalt(I) (22), including an X-ray crystal structure determination of the reaction product with diphenylethyne, the tetraphenylcyclobutadiene complex 30, are presented.
    Additional Material: 1 Ill.
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  • 2
    ISSN: 0009-2940
    Keywords: Acepentalene ; 4,7-dihydro ; complexes ; Degenerate haptotropic rearrangement ; Cobalt complexes ; Iron complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The (cyclopentadienyl)cobalt(I) complex 4 of the 4,7-dihydroacepentaleneThe numbering of the ring system corresponds to the tricyclo-decatetraene nomenclature used in the Exp. Part. Thus, 4,7-substitution would be 2a,4a-substitution in acepentalene numbering. derivative 2b has been prepared by the reaction of the ligand with (cyclopentadienyl)bis(ethene)cobalt(I). NOE experiments indicate a complexation at the convex face of the polyolefinic ligand. 1H-NMR spectra establish a degenerate haptotropic rearrangement with CpCo migration from one diene unit to the adjacent one. The activation energy of this process is estimated to be 15 kcal/mol. An X-ray crystal structure determination of (η4-4,7-dihydroacepentalene)tricarbonyliron derivative 3a shows a distorted coordination of Fe(CO)3 at the convex face of the ligand, too.
    Additional Material: 1 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1651-1656 
    ISSN: 0009-2940
    Keywords: Bicyclo[3.2.0]hepta-1,3-dienyl complexes ; Ring slippage ; Cycloadditions ; Cobalt complexes ; DSC ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title reaction, which was detected by a comparison of the DSC analysis of title compound 2 with that of the corresponding bicyclo[3.3.0]octa-1,3-dienyl complex 3, takes place at 200°C with various dienophiles (dimethyl fumarate, dimethyl maleate, diphenylethyne, N-methylmaleinimide). 3,4-Dimethylenecyclopentenyl complex 12 most likely is the key intermediate of the reaction.
    Additional Material: 1 Ill.
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  • 4
    ISSN: 0009-2940
    Keywords: {[ω-(Phosphanyl)alkyl]cyclopentadienyl}cobalt(I) ; Cobalt complexes ; Bidentate ligand ; Alkynes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An improved synthesis of [(2-phosphanylethyl)cyclopenta-dienyl]cobalt(I) chelate complexes is presented, in which the paramagnetic chloride 3 is a precursor of the ethene complex 4. The latter readily undergoes ligand exchange reactions which in the case of bidendate reagents (1,5-cyclooctadiene, 1,2-bis(diisopropylphosphanyl)ethane, 2,2′-bipyridine, nor-bornadiene) cause a decomplexation of the phosphane arm at room temperature with formation of 7, 5, 6, 8. The ethene ligand in 4 can be replaced by alkynes under equally mild reaction conditions (formation of 9, 11 - 16). The reaction with ethyne results in the formation of vinylidene complex 10. The yields of the reactions with nonaromatic alkynes could be improved by treating 3 with the alkyne in the presence of sodium amalgam. The unsubstituted vinylidene complex 10 and its tert-butyl derivative 17 were obtained by this route in 38 and 40% yield, respectively.
    Additional Material: 1 Ill.
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