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Steric and electronic factors in the promoting activity of diphosphine ligands in cyclohexene hydrocarbomethoxylation catalyzed by palladium acetate

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Abstract

Cyclohexene hydrocarbomethoxylation catalyzed by Pd(OAc)2-p-toluenesulfonic acid-diphosphine systems has been investigated for a wide range of diphosphine structures and concentrations. The factors controlling the activity of the palladium-containing catalysts include the hydrocarbon moiety of the ligand and the mutual arrangement of the phosphine groups. A comparison between the promoting effects of monophosphine and diphosphine ligands has demonstrated that bridged trans-diphosphines are more efficient in kinetic and concentration terms (TOF and P/Pd ratio, respectively). In particular, the promoting activity of diphosphines is one order of magnitude higher than that of triphenylphosphine, and this effect is attained at 8–65 times lower P/Pd ratios. It is discussed how the catalytic properties of the systems depend on the chelate effect and on the geometric compatibility between the diphosphine structure and the arrangement of vacant s and d orbitals of the palladium center.

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Authors and Affiliations

  1. Faculty of Chemistry, Moscow State University, Moscow, 119991, Russia

    I. E. Nifant’ev & V. V. Bagrov

  2. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 119991, Moscow, Russia

    I. E. Nifant’ev & A. N. Tavtorkin

  3. Department of Organic and Biological Chemistry, Tula State Pedagogical University, Tula, 300026, Russia

    S. A. Batashev, N. T. Sevost’yanova, A. A. Vorob’ev & V. A. Aver’yanov

  4. Moscow State Pedagogical University, Moscow, 119991, Russia

    S. A. Toloraya

Authors
  1. I. E. Nifant’ev
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  2. S. A. Batashev
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  3. S. A. Toloraya
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  4. A. N. Tavtorkin
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  5. N. T. Sevost’yanova
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  6. A. A. Vorob’ev
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  7. V. V. Bagrov
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  8. V. A. Aver’yanov
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Correspondence to I. E. Nifant’ev.

Additional information

Original Russian Text © I.E. Nifant’ev, S.A. Batashev, S.A. Toloraya, A.N. Tavtorkin, N.T. Sevost’yanova, A.A. Vorob’ev, V.V. Bagrov, V.A. Aver’yanov, 2012, published in Kinetika i Kataliz, 2012, Vol. 53, No. 4, pp. 483–490.

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Nifant’ev, I.E., Batashev, S.A., Toloraya, S.A. et al. Steric and electronic factors in the promoting activity of diphosphine ligands in cyclohexene hydrocarbomethoxylation catalyzed by palladium acetate. Kinet Catal 53, 462–469 (2012). https://doi.org/10.1134/S0023158412040076

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  • DOI: https://doi.org/10.1134/S0023158412040076

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