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EPR and DFT Study of Copper(II) Complex with 1,10-Phenanthroline as Catalyst for Oxidation of Cyclohexanol with tert-Butyl Hydroperoxide

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Abstract

Copper complex with 1,10-phenanthroline was synthesized by a partially modified method. This complex exhibited relatively high catalytic activity in the oxidation of cyclohexanol with tert-butyl hydroperoxide. The complex was characterized by CW EPR spectroscopy (X-band) at room temperature, and results were compared with calculations carried out by the density functional theory (DFT) method. Partial comparison of the EPR and DFT results with X-ray data proves our hypothesis that the structure and spectral properties of the same copper complex in solutions and in a crystalline state may be different.

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Acknowledgements

The publication was funded by Russian Foundation for Basic Research (Project No. 21-53-54001). This work was performed within the framework of the Program of Fundamental Research of the Russian Academy of Sciences on the research issue of FRCCP RAS No. 47.16. State registration number: AAAA-A20-120021390044-2. Elemental analyses and physical investigations were performed with the financial support from Ministry of Science and Higher Education of the Russian Federation using the equipment of Center for molecular composition studies of INEOS RAS. A.I.K, Y.N.K. and G.B.S. acknowledge the support from the Plekhanov Russian University of Economics. We are also thankful to Ye. N. Degtyarev (N.N. Semenov Federal Research Center for Chemical Physics RAS, Moscow, Russia) for his assistance in some EPR experiments and to Prof. A.Kh. Vorob’ev (Chemistry Department, Lomonosov Moscow State University) provided us his software package.

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Authors and Affiliations

  1. N.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Moscow, Russian Federation

    A. I. Kokorin, E. N. Golubeva, Yu. N. Kozlov & G. B. Shul’pin

  2. Plekhanov Russian University of Economics, Moscow, Russian Federation

    A. I. Kokorin, Yu. N. Kozlov & G. B. Shul’pin

  3. Chemistry Department, M.V. Lomonosov Moscow State University, Moscow, Russian Federation

    E. N. Golubeva

  4. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova St., 119991, Moscow, Russian Federation

    M. M. Vinogradov

Authors
  1. A. I. Kokorin
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  2. E. N. Golubeva
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  3. M. M. Vinogradov
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  4. Yu. N. Kozlov
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  5. G. B. Shul’pin
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Contributions

AIK Supervision, EPR study, validation, writing–reviewing. ENG investigation, software, DFT calculations. MMV synthesis of catalysts. YNK kinetic study. GBS Supervision and writing the manuscript. All authors approve the final version of the manuscript.

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Correspondence to A. I. Kokorin.

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Kokorin, A.I., Golubeva, E.N., Vinogradov, M.M. et al. EPR and DFT Study of Copper(II) Complex with 1,10-Phenanthroline as Catalyst for Oxidation of Cyclohexanol with tert-Butyl Hydroperoxide. Appl Magn Reson 53, 887–894 (2022). https://doi.org/10.1007/s00723-022-01467-x

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  • DOI: https://doi.org/10.1007/s00723-022-01467-x

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