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  Manganese Kβ X-ray Emission Spectroscopy As a Probe of Metal–Ligand Interactions

Beckwith, M. A., Roemelt, M., Collomb, M.-N., DuBoc, C., Weng, T.-C., Bergmann, U., et al. (2011). Manganese Kβ X-ray Emission Spectroscopy As a Probe of Metal–Ligand Interactions. Inorganic Chemistry, 50(17), 8397-8409. doi:10.1021/ic200970t.

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 Creators:
Beckwith, Martha. A.1, 2, Author              
Roemelt, Michael2, 3, Author              
Collomb, Marie-Noëlle4, Author
DuBoc, Carole4, Author
Weng, Tsu-Chien5, Author
Bergmann, Uwe6, Author
Glatzel, Pieter5, Author
Neese, Frank2, 3, Author              
DeBeer, Serena1, 2, Author              
Affiliations:
1Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States, ou_persistent22              
2Research Department Neese, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society, ou_3023879              
3Institut für Physikalische und Theoretische Chemie, Universität Bonn, D-53115 Bonn, Germany, ou_persistent22              
4Université Joseph Fourier Grenoble 1/CNRS, Département de Chimie Moléculaire, UMR-5250, Laboratoire de Chimie Inorganique Redox, Institut de Chimie Moléculaire de Grenoble FR-CNRS-2607, BP-53, 38041 Grenoble Cedex 9, France, ou_persistent22              
5European Synchrotron Radiation Facility, 6 Rue Jules Horowitz, BP 220, Cedex 9, 38043 Grenoble, France, ou_persistent22              
6Linac Coherent Light Source, SLAC National Accelerator Laboratory , Menlo Park, California 94025, United States, ou_persistent22              

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 Abstract: A systematic series of high-spin mononuclear Mn(II), Mn(III), and Mn(IV) complexes has been investigated by manganese Kβ X-ray emission spectroscopy (XES). The factors contributing to the Kβ main line and the valence to core region are discussed. The Kβ main lines are dominated by 3p–3d exchange correlation (spin state) effects, shifting to lower energy upon oxidation of Mn(II) to Mn(III) due to the decrease in spin state from S = 5/2 to S = 2, whereas the valence to core region shows greater sensitivity to the chemical environment surrounding the Mn center. A density functional theory (DFT) approach has been used to calculate the valence to core spectra and assess the contributions to the energies and intensities. The valence spectra are dominated by manganese np to 1s electric dipole-allowed transitions and are particularly sensitive to spin state and ligand identity (reflected primarily in the transition energies) as well as oxidation state and metal–ligand bond lengths (reflected primarily in the transition intensities). The ability to use these methods to distinguish different ligand contributions within a heteroleptic coordination sphere is highlighted. The similarities and differences between the current Mn XES study and previous studies of Fe XES investigations are discussed. These findings serve as an important calibration for future applications to manganese active sites in biological and chemical catalysis.

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Language(s): eng - English
 Dates: 2011-05-092011-08-012011-09-05
 Publication Status: Published in print
 Pages: 13
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ic200970t
 Degree: -

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Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 50 (17) Sequence Number: - Start / End Page: 8397 - 8409 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669