Mechanism of oxidative carbonylation of phenylacetylene and methylacetylene. Generation and experimental discrimination of hypotheses |
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| Authors: | L G Bruk S N Gorodskii A V Zeigarnik R E Valdés-Peréz O N Temkin |
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| Institution: | (1) M. V. Lomonosov Moscow State Academy of Fine Chemical Technology, 86 prosp. Vernadskogo, 117571 Moscow, Russian Federation;(2) Computer Science Department, Carnegie Mellon University, 15213 Pittsburgh, PA, USA |
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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.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 882–889, May, 1999. |
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| Keywords: | phenylacetylene oxidative carbonylation reaction mechanisms catalysts palladium complexes alkynylcarboxylic acid ester methyl phenylpropiolate kinetic isotope effect |
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