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  • 1: advanced search Author, Corporation: Guet, C.   :    :   —  7 hits    Redo Search Permalink feed icon
  • 2: advanced search Author, Corporation: Miller, Kenneth J.   :    :   —  32 hits    Redo Search Permalink feed icon
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  • Articles: DFG German National Licenses  (2)
  • Allene complexes  (1)
  • Cycloheptatrienyl, carbene derivatives of  (1)
  • 1
    Electronic Resource
    Electronic Resource
    Organische Synthesen mit Übergangsmetallkomplexen, 71. Methylcarben-Komplexe von Chrom und Wolfram mit Cycloheptatrienyl-, Cyclohexadienyl[Fe(CO)3]- und Cycloheptadienyl[Fe(CO)3]-Resten als α-Substituenten (1994)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 731-738 
    Details
    ISSN: 0009-2940
    Keywords: Methylcarbene complexes of chromium and tungsten ; Cyclohexadienyl tricarbonyliron, carbene derivatives of ; Cycloheptadienyl tricarbonyliron, carbene derivatives of ; Cycloheptatrienyl, carbene derivatives of ; Enol ether, elimination from carbene complexes ; Spirocyclopropanes, elimination from carbene complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organic Syntheses via Transition Metal Complexes, 71[1].  -  Methylcarbene Complexes of Chromium and Tungsten with Cycloheptatrienyl-, Cyclohexadienyl[Fe(CO)3]- and Cycloheptadienyl[Fe(CO)3] SubstituentsMethylcarbene complexes LnM=C(OEt)CH3 1 [LnM = (CO)5Cr, (CO)5W] react with tropylium tetrafluoroborate (2a) or coordinated olefins of [C6H7Fe(CO)3]BF4 (2c), [C7H9Fe-(CO)3]BF4 (2d), and [C7H7Fe2(CO)6]BF4 (2d) in the presence of Et3N to give complexes LnM=C(OEt)CH2R 3a-e and LnM=C(OEt)CHR2 7a-d by substitution of one or two α-hydrogen atoms. The trimetallic WFe2 carbene complexes 7c, d derived from 1b with 2c, d form three stereoisomers each, which are fully characterized spectroscopically, (R*,R*,S*)-7c additionally also by an X-ray structure analysis, Ligand elimination from 3 and 7 may involve a-and/or β-hydrogen transfer reactions: Thus enol ethers (Z/E)-6 are eliminated from α-monosubstituted methylcarbene complexes 3a, c, d in yields of 62-90% by a pyridine-induced transfer of an α-hydrogen to the carbene carbon atom; with increasing steric demand of R the elimination of the (Z) isomer (Z)-6 from 3 is favoured over the formation of the (E) isomer (E)-6. The enol ether 10 becomes a minor side product in the pyridine-induced ligand elimination from α-disubstituted complexes 7a, b. In these cases the spirocyclopropane 8 is formed as the main product (60-82%) besides the 4,5-homotropylidene 9 by a conformationally directed β-hydrogen transfer reaction.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19941270424
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    Paper (German National Licenses)
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  • 2
    Electronic Resource
    Electronic Resource
    Organic Syntheses via Transition Metal Complexes, 74[1] Novel Phosphonium Allenide and 2-Phosphanylethenyl Carbene Chromium and Tungsten Complexes (1994)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 2475-2482 
    Details
    ISSN: 0009-2940
    Keywords: Vinylcarbene complexes ; Chromium complexes ; Tungsten complexes ; Phosphorus ylide complexes ; Alkynylcarbene complexes ; Allene complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alkynylcarbene complexes (CO)5M≡C(OEt)-C≡C—R 1 (M = Cr, W; R = Ph, tBu, SiMe3) readily add tertiary phosphanes PPhR2′ 4 (R′ = Ph, Me) to form stable zwitterionic phosphonium allenide complexes (CO)5M--C(OEt) = C≡C(R)-P+PhR2′ 5. Complex 5a (M = Cr, R = R′ = Ph) was characterized by X-ray diffraction. The addition of secondary phosphanes PHR2 6 to 1 affords red (2-phosphanyl ethenyl)-carbene complexes (CO)5M≡C(OEt)-CH≡C(R)-PR2 (E)-8 (R = tBu, cC6H11, Ph) in 34-89% isolated yields. Dinuclear complexes (CO)5M≡C(OEt)-CH≡C(R)-P(R2)M(CO)5 (E)-9 are obtained as byproducts. Compounds (E)-8b (M = Cr, R = cC6H11) and (E)-9i (M = Cr, R = Ph) were characterized by X-ray analyses.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19941271218
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    Paper (German National Licenses)
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