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  • Arene complexes  (4)
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  • 1
    Electronic Resource
    Electronic Resource
    Sidechain Functionalizations by Cuprate Additions to Phosphorylallenyl-Substituted Arenetricarbonylchromium Complexes (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 225-233 
    Details
    ISSN: 1434-1948
    Keywords: Arene complexes ; Chromium ; Sidechain functionalization ; Allenes ; Cuprates ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cuprate addition to (arene)Cr(CO)3-substituted phosphorylallenes 1 gives rise to the regioselective formation of complexed allylphosphane oxide derivatives 3a-c and allylphosphonate derivatives 3d-j in good yields. In the case of racemic planar chiral ortho-substituted complexed (arylallenyl)phosphonates 1c, d the protonation of the intermediate allyl anion proceeds diastereoselectively due to the hindered rotation around the Cipso-Cα bond. This diastereoselective protonation is discussed on the basis of the conformational analysis as deduced from the X-ray structure analyses of the allenylphosphonate 1d and the allylphosphonates 3i, j.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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    Paper (German National Licenses)
  • 2
    Electronic Resource
    Electronic Resource
    Synthesis and Substituent Interactions of Tricarbonylchromium-complexed Arylalkynylbenzenes  -  Novel Organometallic Push-pull ChromophoresDedicated to Prof. Dr. Rudolf Gompper on the occasion of his 70th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1433-1440 
    Details
    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
    URL: http://dx.doi.org/10.1002/cber.19961291206
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  • 3
    Electronic Resource
    Electronic Resource
    Palladium-Copper-Catalyzed Coupling of Tricarbonylchromium-Complexed Phenylacetylene with Iodoarenes - A Facile Access to Alkynyl-Bridged Cr(CO)3-Complexed Benzenes (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 607-613 
    Details
    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
    URL: http://dx.doi.org/10.1002/cber.19961290604
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  • 4
    Electronic Resource
    Electronic Resource
    Synthesis and Structure of Allenyl-Substituted η6-Benzene(tricarbonyl)-chromium Complexes (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1135-1139 
    Details
    ISSN: 0009-2940
    Keywords: Arene complexes ; Chromium ; Allenes ; Rearrangements ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Cr(CO)3-complexed η6-phenylpropargylic alcohols 3 react in a displacement rearrangement with thionyl chloride or chlorodiphenylphosphane to give the chloro- or phosphoryl allenyl substituted η6-phenyl complexes 4 and 6, respectively. In the X-ray crystal structure of the novel organometallic allenic derivatives 4b and 6b the vicinal chloro or phosphoryl substituent and the benzene(tricarbonyl)chromium fragment are arranged coplanarily. Palladium/copper-catalyzed couplings of the chloroallene 4b with terminal alkynes disclose a facile access to ynallene derivatives 8, novel carbon-rich organometallic π-systems.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300816
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