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Mechanism of oxidative carbonylation of phenylacetylene and methylacetylene. Generation and experimental discrimination of hypotheses

  • Physical Chemistry
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Abstract

Formal and informal methods for advancing hypotheses on mechanisms were used in a study of the oxidative carbonylation of phenylacetylene to methyl phenylpropiolate catalyzed by the PdCl2−CuCl−CuCl2 system. The hypotheses remaining after discrimination and consistent with all experimental data include the steps of formation of the CuI alkynyl complex, transfer of the phenylethynyl group from CuI to PdII, insertion of carbon monoxide into a Pd−C or Pd−OMe bond of the PdII σ-alkynyl complex. Comparison of the formal and informal methods for advancing hypotheses confirmed a higher effeciency of the first method.

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Authors and Affiliations

  1. M. V. Lomonosov Moscow State Academy of Fine Chemical Technology, 86 prosp. Vernadskogo, 117571, Moscow, Russian Federation

    L. G. Bruk, S. N. Gorodskii, A. V. Zeigarnik & O. N. Temkin

  2. Computer Science Department, Carnegie Mellon University, 15213, Pittsburgh, PA, USA

    R. E. Valdés-Peréz

Authors
  1. L. G. Bruk
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  2. S. N. Gorodskii
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  3. A. V. Zeigarnik
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  4. R. E. Valdés-Peréz
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  5. O. N. Temkin
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Additional information

Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 882–889, May, 1999.

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Bruk, L.G., Gorodskii, S.N., Zeigarnik, A.V. et al. Mechanism of oxidative carbonylation of phenylacetylene and methylacetylene. Generation and experimental discrimination of hypotheses. Russ Chem Bull 48, 873–880 (1999). https://doi.org/10.1007/BF02494629

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  • DOI: https://doi.org/10.1007/BF02494629

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