On the Way to Carbene and Carbyne Complexes*

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The chapter focuses on carbene andcarbyne complexes. If one of the hydrogen atoms in an alkane hydrocarbon, such as ethane, is formally replaced by a metal atom, an organometallic compound in which the organic entity is bonded to the metal by a σ-bond is obtained. If a system with 2 carbon atoms bonded to each other by a double bond, i.e., an alkene molecule, is considered, a number of separate paths leading to organometallic derivatives are recognized. One path involves the replacement of a substituent by a metal atom and leads to σ compounds that are exemplified by vinyl-lithium derivatives. If molecules with a carbon-carbon triple bond of the type that exists in alkynes are considered, then it is realized that there also are three possible paths to metal-containing derivatives. The chapter discusses various properties of transition metal-carbene complexes such as preparation of the first carbene complexes, bonding concepts, and spectroscopic findings. It also presents various properties of transition metal-carbyne complexes such as preparation of the first carbyne complexes and x-ray structural analyses.

References (100)

  • G. Wilkinson et al.

    Progr. Inorg. Chem.

    (1959)
  • E.O. Fischer et al.

    Angew. Chem.

    (1970)

    Angew. Chem., Int. Ed. Engl.

    (1970)
  • E.O. Fischer et al.

    Chem. Ber.

    (1972)
  • E.O. Fischer et al.

    Chem. Ber.

    (1968)
  • E.O. Fischer et al.

    Chem. Ber.

    (1971)
  • E.O. Fischer

    Pure Appl. Chem.

    (1970)

    Pure Appl. Chem.

    (1972)
  • G. Kreis et al.

    Chem. Ber.

    (1973)
  • C.G. Kreiter

    Angew. Chem.

    (1968)

    Angew. Chem., Int. Ed. Engl.

    (1968)
  • E.O. Fischer, S. Walz, G. Kreis,...
  • U. Schubert et al.

    Chem. Ber.

    (1973)
  • E.O. Fischer et al.

    J. Organometal. Chem.

    (1969)
  • E.O. Fischer, K. Richter,...
  • E.O. Fischer, E.W. Meineke,...
  • E.O. Fischer, D. Plabst,...
  • R. Bunsen

    Liebigs. Ann. Chem.

    (1842)
  • E. Frankland Liebigs Ann. Chem. 21 171...

    Liebigs Ann. Chem.

    (1855)
  • V. Grignard

    C. R. Acad. Sci.

    (1900)
  • K. Ziegler

    Angew. Chetn.

    (1964)
  • E.O. Fischer et al.

    “Metal-π-Complexes with Di- and Oligo-olefinic Ligands”

    (1966)
  • M. Herberhold

    “Metal-π-Complexes,”

    Complexes with Monoolefinic Ligands.

    (1972)
  • W.C. Zeise

    Poggendorfs Ann.

    (1827)
  • E.O. Fischer et al.

    Advan. Inorg. Chetn. Radiochem.

    (1959)

    Angew. Chem.

    (1961)
    E.O. Fischer

    Angew. Chem.

    (1955)
  • E.O. Fischer et al.

    Z. Natarforsch. B

    (1955)
  • W. Hiibel
  • E.O. Fischer et al.

    Angew. Chem.

    (1964)

    Angew. Chem., Int. Ed. Engl.

    (1964)
  • M. Ryang et al.

    Bull. Chem. Soc. Jap.

    (1964)
  • E.O. Fischer et al.

    J. Organometal. Chem.

    (1973)
  • R. Aumann et al.

    Chem. Ber.

    (1968)
  • H. Meerwein et al.

    J. Prakt, Chem.

    (1937)
    H. Meerwein et al.

    ibid.

    (1940)
  • E.O. Fischer et al.

    Chem. Ber.

    (1967)
  • E.O. Fischer et al.

    Angew. Chem.

    (1971)

    Angew. Chem., Int. Ed. Engl.

    (1971)
  • E.O. Fischer et al.

    J. Organometal. Chem.

    (1971)
  • E.O. Fischer et al.

    J. Organometal. Chem.

    (1972)
  • E.O. Fischer et al.

    Chem. Ber.

    (1972)
  • J.W. Wilson et al.

    J. Organometal. Chem.

    (1973)
  • E.O. Fischer et al.

    Chem. Ber.

    (1969)
  • E.O. Fischer et al.

    Chem. Ber.

    (1972)
  • E.O. Fischer et al.

    Chem. Ber.

    (1972)
  • E.O. Fischer et al.

    Chem. Ber.

    (1969)
  • O.S. Mills et al.

    J. Chem. Soc. A

    (1968)
  • F.A. Cotton et al.

    Inorg. Chem.

    (1966)
  • E. Moser et al.

    J. Organometal. Chem.

    (1968)
  • C.G. Kreiter et al.

    Angew. Chem.

    (1969)

    Angew. Chem., Int. Ed. Engl.

    (1969)
  • C.G. Kreiter et al.

    Chem. Ber.

    (1970)
  • J.A. Connor et al.

    J. Chem. Soc. A

    (1969)
  • E.O. Fischer et al.

    Chem. Ber.

    (1971)
  • N.J. Hawkins et al.

    J. Chem. Phys.

    (1955)
  • C.G. Kreiter et al.

    Angew. Chern.

    (1972)

    Angew. Chem., Int. Ed. Engl.

    (1972)
  • D.J. Cardin et al.

    Chem. Rev.

    (1972)
  • F.A. Cotton et al.

    Progr. Inorg. Chem.

    (1972)
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    *

    A Nobel lecture translated by P. Legzdins and G.O. Wiedersatz, Technical Uni-versity, Munich. Copyright © The Nobel Foundation, 1974.

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