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Theoretical interpretation of the role of the ionic liquid phase in the (R)-Ru-BINAP catalyzed hydrogenation of methylacetoacetate

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Abstract

Recently, the work focusing on the role of alkyl chain length in the N[R,222][Tf2N] ionic liquids and its reflection in the kinetic parameters of stereoselective hydrogenation of methylacetoacetate over (R)-[RuCl(binap)(p-cymene)]Cl complex was reported. Irregular trends in the principle parameter of enantioselectivity were observed. Here, a possible theoretical explanation of such irregular trends elucidated with the help of molecular simulations methods is presented. A stepwise approach is proposed for evaluating the energetically most stable conformers of a series of individual N[R,222][Tf2N] for the interpretation of selectivity-structure effects observed experimentally. Initially, Monte Carlo molecular mechanics was used followed by a semi-empirical PM3 method to elucidate also the characteristic thermodynamic functions of state and theoretical molecular spectra. The density functional theory was finally applied. The specific absolute entropy data revealed that due to the partition of the cation and anion twisted closer approach the ionic liquids N[8,222][Tf2N] and N[12,222][Tf2N] may stabilize the structures of the (R)-[RuCl(binap)(p-cymene)]Cl complex.

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Acknowledgments

Authors gratefully acknowledge the financial contribution of the Ministry of Industry and Trade of the Czech Republic, Project Grant No. FR-TI3/057. Academy of Sciences of the Czech Republic is also cordially acknowledged for supporting the bilateral CZ-UK cooperation project with Bangor University, UK.

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Authors and Affiliations

  1. Institute of Chemical Process Fundamentals ASCR, Rozvojova 2, 165 02, Prague 6, Czech Republic

    Pavel Dytrych, Petr Kluson & Olga Solcova

  2. School of Chemistry, Bangor University, Bangor, Gwynedd, LL57 2DG, UK

    Morwena Slater

Authors
  1. Pavel Dytrych
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  2. Petr Kluson
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  3. Morwena Slater
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  4. Olga Solcova
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Correspondence to Petr Kluson.

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Dytrych, P., Kluson, P., Slater, M. et al. Theoretical interpretation of the role of the ionic liquid phase in the (R)-Ru-BINAP catalyzed hydrogenation of methylacetoacetate. Reac Kinet Mech Cat 111, 475–487 (2014). https://doi.org/10.1007/s11144-013-0659-x

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