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Alkyne-vinylidene coupling in the reactions of the alkyne complex Os3(μ-CO)(CO)9(μ3-Me3C2Me) with Me3SiC≡CR (R=Me, Bun). The structure and stereodynamic behavior of clusters Os3(CO)9{μ3-C(SiMe3)=C(Me)C=C(SiMe3)=C(Me)C=C(SiMe3)R} containing an osmacyclobutene moietycontaining an osmacyclobutene moiety

  • Organometallic Chemistry
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Russian Chemical Bulletin Aims and scope

Abstract

Reactions of the alkyne cluster Os3(μ-CO)(CO)9(μ3-Me3C2Me) with alkynes Me3SiC≡CR (R=Me, Bun) in refluxing hexane result in the formation of clusters Os3(CO)9{μ3-C(SiMe3)=C(Me)C=C(SiMe3)=C(Me)C=C(SiMe3)R} (2a: R=Me;3a: R=Bun). The dienediyl ligand in these complexes is formed by alkyne-vinylidene coupling, with vinylidene generated in the course of reaction from the alkyne molecule by the acetylene-vinylidene rearrangement involving a 1,2-shift of the Me3Si group. The structure of cluster3a was determined by X-ray structural analysis. The dienediyl ligand is coordinated to three metal atoms of the cluster framework by two π-ethylene bonds with two osmium atoms and two σ-bonds with the third osmium atom with the formation of the osmacyclobutene moiety. The1H and13C NMR study of13CO-enriched samples of clusters2a and3a revealed the stereochemical nonrigidity of these molecules due to the exchange of the hydrocarbon and carbonyl ligands.

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Authors and Affiliations

  1. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation

    A. A. Koridze, A. M. Sheloumov, F. M. Dolgushin, A. I. Yanovsky, P. V. Petrovskii & O. L. Tok

Authors
  1. A. A. Koridze
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  2. A. M. Sheloumov
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  3. F. M. Dolgushin
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  4. A. I. Yanovsky
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  5. P. V. Petrovskii
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  6. O. L. Tok
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1024–1029, May, 1998.

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Koridze, A.A., Sheloumov, A.M., Dolgushin, F.M. et al. Alkyne-vinylidene coupling in the reactions of the alkyne complex Os3(μ-CO)(CO)9(μ3-Me3C2Me) with Me3SiC≡CR (R=Me, Bun). The structure and stereodynamic behavior of clusters Os3(CO)9{μ3-C(SiMe3)=C(Me)C=C(SiMe3)=C(Me)C=C(SiMe3)R} containing an osmacyclobutene moietycontaining an osmacyclobutene moiety. Russ Chem Bull 47, 995–1000 (1998). https://doi.org/10.1007/BF02498174

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  • DOI: https://doi.org/10.1007/BF02498174

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