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  Structural and Spectroscopic Evidence for a Side-on Fe(III)–Superoxo Complex Featuring Discrete O–O Bond Distances

Pan, H.-R., Chen, H.-J., Wu, Z.-H., Ge, P., Ye, S., Lee, G.-H., et al. (2021). Structural and Spectroscopic Evidence for a Side-on Fe(III)–Superoxo Complex Featuring Discrete O–O Bond Distances. JACS Au, 1(9), 1389-1398. doi:10.1021/jacsau.1c00184.

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 Creators:
Pan, Hung-Ruei1, Author
Chen, Hsin-Jou1, Author
Wu, Zong-Han1, Author
Ge, Pu2, Author
Ye, Shengfa3, 4, Author              
Lee, Gene-Hsiang5, Author
Hsu, Hua-Fen1, Author
Affiliations:
1Department of Chemistry, National Cheng Kung University, Tainan 701, Taiwan, ou_persistent22              
2School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, P. R. China, ou_persistent22              
3State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, P. R. China, ou_persistent22              
4Research Group Ye, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541708              
5Department of Chemistry, National Taiwan University, Taipei 106, Taiwan, ou_persistent22              

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 Abstract: The O–O bond length is often used as a structural indicator to determine the valence states of bound O2 ligands in biological metal–dioxygen intermediates and related biomimetic complexes. Here, we report very distinct O–O bond lengths found for three crystallographic forms (1.229(4), 1.330(4), 1.387(2) Å at 100 K) of a side-on iron–dioxygen species. Despite their different O–O bond distances, all forms possess the same electronic structure of Fe(III)–O2•–, as evidenced by their indistinguishable spectroscopic features. Density functional theory and ab initio calculations, which successfully reproduce spectroscopic parameters, predict a flat potential energy surface of an η2-O2 motif binding to the iron center regarding the O–O distance. Therefore, the discrete O–O bond lengths observed likely arise from differential intermolecular interactions in the second coordination sphere. The work suggests that the O–O distance is not a reliable benchmark to unequivocally identify the valence state of O2 ligands for metal–dioxygen species in O2-utilizing metalloproteins and synthetic complexes.

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Language(s): eng - English
 Dates: 2021-04-252021-08-312021-09-27
 Publication Status: Published online
 Pages: 10
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacsau.1c00184
 Degree: -

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Title: JACS Au
  Abbreviation : JACS Au
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 1 (9) Sequence Number: - Start / End Page: 1389 - 1398 Identifier: ISSN: 2691-3704
CoNE: https://pure.mpg.de/cone/journals/resource/2691-3704