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  • 1
    ISSN: 0009-2940
    Keywords: Arene complexes ; Chromium compounds ; Substituent effects ; Push-pull chromophores ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tricarbonylchromium complexes chlorobenzene 1 reacts with terminal alkynes 2 through a palladium-copper-catalyzed coupling to give a variety of Cr(CO)3-complexed phenylethynyl arenes, heteroarenes and ferrocene 3 in good to excellent yield. Due to the electron-withdrawing nature of the Cr(CO)3 group these novel complexes can be regarded as organometallic push-pull chromophores. Analogously, the corresponding free ligands 4 (phenylethynyl arenes, heteroarenes and ferrocene) were synthesized by coupling iodobenzene and 2. The crystal structure analysis of the singly Cr(CO)3-complexed tolane 3e reveals a strong deviation from coplanarity of both phenyl rings by an angle of 50.9(2)° presumably due to crystal packing. Correlations are established between selected substituent parameters (σP, σI, σR, σP+ and Δπ) and the carbonyl carbon resonances in the 13C-NMR spectra for the complexes 3. The overall electronic substituent effect is transmitted to the carbonyl groups by both mesomeric and inductive mechanisms. The push-pull complexes 3 display relatively small negative solvochromicities of longest wavelength absorption band (MLCT band).
    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 129 (1996), S. 607-613 
    ISSN: 0009-2940
    Keywords: Arene complexes ; Chromium compounds ; Alkynes ; Catalysis ; Coupling reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The palladium-copper-catalyzed coupling of the tricarbonyl-chromium-complexed chlorobenzene 1 with (trimethylsilyl)-acetylene gives tricarbonyl{η6-[(trimethylsilyl)ethynyl]-benzene}chromium(0) (2) in high yield. After desilylation of 2 tricarbonyl[η6-(ethynylbenzene)]chromium(0) (3) is obtained quantitatively. Using the palladium-copper-catalyzed methodology, we can readily introduce Cr(CO)3-complexed phenylethynyl units by a multifold coupling of 3 with iodobenzene, 1,2-, 1,3-, 1,4-di- and 1,3,5-tiiodobenzene (4a-e) or 1 to give polynuclear Cr(CO)3-complexed (phenylethynyl)benzenes 5a-e and doubly Cr(CO)3-complexed tolane 6 in good to moderate yield. The crystal structure analyses of μ3-{η6:η6:η6[1,3,5-benzenetriyltris(2,1-ethynediyl)]tris(benzene)}tris[tricarbonylchromium(0)] (5e) and μ-{η6:η6-[1,2-ethynediylbis(benzene)]}bis[tricarbonylchromium(0)] (6) reveal that the tricarbonylchromium tripods in the same molecule are arranged in antiparallel syn-eclipsed conformations. The Eglington coupling of 3 affords a doubly Cr(CO)3-complexed diphenylbutadiyne 7 in excellent yield.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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