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Ebbe Nordlander. Portrait.

Ebbe Nordlander

Professor

Ebbe Nordlander. Portrait.

Enhanced Understanding of Structure-Function Relationships for Oxomanganese(IV) Complexes

Author

  • Priya Singh
  • Yuri Lee
  • Jaycee R. Mayfield
  • Reena Singh
  • Melissa C. Denler
  • Shannon D. Jones
  • Victor W. Day
  • Ebbe Nordlander
  • Timothy A. Jackson

Summary, in English

A series of manganese(II) and oxomanganese(IV) complexes supported by neutral, pentadentate ligands with varied equatorial ligand-field strength (N3pyQ, N2py2I, and N4pyMe2) were synthesized and then characterized using structural and spectroscopic methods. On the basis of electronic absorption spectroscopy, the [MnIV(O)(N4pyMe2)]2+ complex has the weakest equatorial ligand field among a set of similar MnIV-oxo species. In contrast, [MnIV(O)(N2py2I)]2+ shows the strongest equatorial ligand-field strength for this same series. We examined the influence of these changes in electronic structure on the reactivity of the oxomanganese(IV) complexes using hydrocarbons and thioanisole as substrates. The [MnIV(O)(N3pyQ)]2+ complex, which contains one quinoline and three pyridine donors in the equatorial plane, ranks among the fastest MnIV-oxo complexes in C-H bond and thioanisole oxidation. While a weak equatorial ligand field has been associated with high reactivity, the [MnIV(O)(N4pyMe2)]2+ complex is only a modest oxidant. Buried volume plots suggest that steric factors dampen the reactivity of this complex. Trends in reactivity were examined using density functional theory (DFT)-computed bond dissociation free energies (BDFEs) of the MnIIIO-H and MnIV ≡ O bonds. We observe an excellent correlation between MnIV≡O BDFEs and rates of thioanisole oxidation, but more scatter is observed between hydrocarbon oxidation rates and the MnIIIO-H BDFEs.

Department/s

  • Chemical Physics
  • LU Profile Area: Light and Materials

Publishing year

2023

Language

English

Pages

18357-18374

Publication/Series

Inorganic Chemistry

Volume

62

Issue

45

Document type

Journal article

Publisher

The American Chemical Society (ACS)

Topic

  • Theoretical Chemistry (including Computational Chemistry)
  • Inorganic Chemistry

Status

Published

ISBN/ISSN/Other

  • ISSN: 0020-1669