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Ebbe Nordlander. Portrait.

Ebbe Nordlander

Professor

Ebbe Nordlander. Portrait.

C-H Bond Oxidation by MnIV-Oxo Complexes : Hydrogen-Atom Tunneling and Multistate Reactivity

Author

  • Priya Singh
  • Allyssa A. Massie
  • Melissa C. Denler
  • Yuri Lee
  • Jaycee R. Mayfield
  • Markell J.A. Lomax
  • Reena Singh
  • Ebbe Nordlander
  • Timothy A. Jackson

Summary, in English

The reactivity of six MnIV-oxo complexes in C-H bond oxidation has been examined using a combination of kinetic experiments and computational methods. Variable-temperature studies of the oxidation of 9,10-dihydroanthracene (DHA) and ethylbenzene by these MnIV-oxo complexes yielded activation parameters suitable for evaluating electronic structure computations. Complementary kinetic experiments of the oxidation of deuterated DHA provided evidence for hydrogen-atom tunneling in C-H bond oxidation for all MnIV-oxo complexes. These results are in accordance with the Bell model, where tunneling occurs near the top of the transition-state barrier. Density functional theory (DFT) and DLPNO-CCSD(T1) computations were performed for three of the six MnIV-oxo complexes to probe a previously predicted multistate reactivity model. The DFT computations predicted a thermal crossing from the 4B1 ground state to a 4E state along the C-H bond oxidation reaction coordinate. DLPNO-CCSD(T1) calculations further confirm that the 4E transition state offers a lower energy barrier, reinforcing the multistate reactivity model for these complexes. We discuss how this multistate model can be reconciled with recent computations that revealed that the kinetics of C-H bond oxidation by this set of MnIV-oxo complexes can be well-predicted on the basis of the thermodynamic driving force for these reactions.

Department/s

  • Chemical Physics
  • LU Profile Area: Light and Materials

Publishing year

2024

Language

English

Pages

7754-7769

Publication/Series

Inorganic Chemistry

Volume

63

Issue

17

Document type

Journal article

Publisher

The American Chemical Society (ACS)

Topic

  • Theoretical Chemistry (including Computational Chemistry)
  • Physical Chemistry (including Surface- and Colloid Chemistry)

Status

Published

ISBN/ISSN/Other

  • ISSN: 0020-1669