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  Electronic and Molecular Structure of the Transient Radical Photocatalyst Mn(CO)5 and Its Parent Compound Mn2(CO)10

Cho, H., Hong, K., Strader, M. L., Lee, J. H., Schoenlein, R. W., Huse, N., et al. (2016). Electronic and Molecular Structure of the Transient Radical Photocatalyst Mn(CO)5 and Its Parent Compound Mn2(CO)10. Inorganic Chemistry, 55(12), 5895-5903. doi:10.1021/acs.inorgchem.6b00208.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-002B-0988-3 Version Permalink: http://hdl.handle.net/11858/00-001M-0000-002B-0989-1
Genre: Journal Article

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 Creators:
Cho, Hana1, 2, Author
Hong, Kiryong1, 2, Author
Strader, Matthew L.2, Author
Lee, Jae Hyuk2, Author
Schoenlein, Robert W.2, Author
Huse, Nils3, 4, 5, Author              
Kim, Tae Kyu1, Author
Affiliations:
1Department of Chemistry and Chemistry Institute of Functional Materials, Pusan National University, Busan 46241, Republic of Korea, ou_persistent22              
2Ultrafast X-ray Science Laboratory, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States, ou_persistent22              
3Ultrafast Molecular Dynamics, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_1938289              
4Department of Physics, University of Hamburg, 22761 Hamburg, Germany, ou_persistent22              
5Center for Free-Electron Laser Science, 22761 Hamburg, Germany, ou_persistent22              

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 Abstract: We present a time-resolved X-ray spectroscopic study of the structural and electronic rearrangements of the photocatalyst Mn2(CO)10 upon photocleavage of the metal–metal bond. Our study of the manganese K-edge fine structure reveals details of both the molecular structure and valence charge distribution of the photodissociated radical product. Transient X-ray absorption spectra of the formation of the Mn(CO)5 radical demonstrate surprisingly small structural modifications between the parent molecule and the resulting two identical manganese monomers. Small modifications of the local valence charge distribution are decisive for the catalytic activity of the radical product. The spectral changes reflect altered hybridization of metal-3d, metal-4p, and ligand-2p orbitals, particularly loss of interligand interaction, accompanied by the necessary spin transition due to radical formation. The spectral changes in the manganese pre- and main-edge region are well-reproduced by time-dependent density functional theory and ab initio multiple scattering calculations.

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Language(s): eng - English
 Dates: 2016-01-282016-06-012016-06-20
 Publication Status: Published in print
 Pages: 9
 Publishing info: -
 Table of Contents: -
 Rev. Method: Peer
 Identifiers: DOI: 10.1021/acs.inorgchem.6b00208
 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: 55 (12) Sequence Number: - Start / End Page: 5895 - 5903 Identifier: ISSN: 0020-1669
CoNE: /journals/resource/0020-1669