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Zeitschrift für Naturforschung B

A Journal of Chemical Sciences

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Volume 40, Issue 5 (May 1985)


Die oxidative Addition von NickeI(0)-KompIexen an Kohlenstoff-Kohlenstoff-Bindungen im Cyclobutadien. Zur Frage der Überführbarkeit von Cyclobutadien-Nickel(O)-Komplexen in Nickelaringe / Oxidative Addition of Nickel(O) Complexes to Carbon-Carbon Bonds in Cyclobutadiene. The Question of the Interconvertibility of Cyclobutadiene-nickel(O) Complexes and the Nickelaring Systems

John J. Eisch
  • Department of Chemistry, State University of New York at Binghamton, Binghamton, New York, 13901, U.S.A.
/ Andrzej M. Piotrowski
  • Department of Chemistry, State University of New York at Binghamton, Binghamton, New York, 13901, U.S.A.
/ Allen A. Aradi
  • Department of Chemistry, State University of New York at Binghamton, Binghamton, New York, 13901, U.S.A.
/ Carl Krüger
  • Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-4330 Mülheim a. d. Ruhr, F. R.G
/ Maria J. Romão
  • Neue Anschrift: Laboratorio de Quimica Organica, Instituto Superior Technico, Av. Rovisco Pais, 1096-Lisboa Codex, Portugal
Published Online: 2014-06-02 | DOI: https://doi.org/10.1515/znb-1985-0511


Bis(triethylphosphine)(η4-tetraphenylcyclobutadiene)nickel (4) was synthesized by the reduction of (η4-tetraphenylcyclobutadiene)nickel(II)bromide (3) with t-butyllithium in the presence of Et3P, and its structure was determined by X-ray crystallography. Furthermore, its reactivity towards CO, CH3CO2H, PhC≡CPh, LiAlH4 and O2 were investigated. 1,1-Bis(triethylphos-phine)-2,3,4,5-tetraphenylnickelole (14) was synthesized from (E,E)-1,4-dilithio-1,2,3,4-tetraphenyl-1,3-butadiene (15) and bis(triethylphosphine)nickel(II)bromide. Since the resulting crystals of the nickelole were not suitable for X-ray structure determination, the compound was characterized by elemental analyses, spectral data and carbonylation to yield tetraphenylcyclo-pentadienone (6).

Analogous reductions of (η4 -tetraphenylcyclobutadiene)nickel(II)bromide (3) in the presence of Ph3P or Ph2PCH2CH2PPh2 , followed by carbonylation, led to 6 in 40% yield, demonstrating that about half of the cyclobutadiene rings in 3 undergo cleavage upon reduction to give the nickelole.

Reactions of the dilithium reagent 15 with NiBr2 complexed with Me2PCH2CH2PMe2 ,Ph3P or Et2PCH2CH2PEt2 , led to the formation of thermolabile nickeloles, as demonstrated by carbonylàtion which yielded 6. Warming of the nickeloles and subsequent treatment with CH3CO2H led to the formation of 1,2,3,4,5,6,7,8-octaphenyl-1,3,5,7-octatetraene (8) and, in one case, octaphenyl-cyclooctatetraene (5).

The relevance of these findings to the mechanism of the Reppe nickel-catalyzed oligomerization of alkynes is discussed.

: Insertion Reaction; Oxidative Addition; Cyclobutadiene-Nickel(O) Complexes; Nickelacyclopentadiene; Nickelole

About the article

Received: 1985-01-15

Published Online: 2014-06-02

Published in Print: 1985-05-01

Citation Information: Zeitschrift für Naturforschung B, ISSN (Online) 1865-7117, ISSN (Print) 0932-0776, DOI: https://doi.org/10.1515/znb-1985-0511. Export Citation

© 1946 – 2014: Verlag der Zeitschrift für Naturforschung. This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License. (CC BY-NC-ND 3.0)

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