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Synthesis of Hetero-multinuclear Metal Complexes by Site-Selective Redox Switching and Transmetalation on a Homo-multinuclear Complex

  • Hitoshi Ube
    Hitoshi Ube
    Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
    More by Hitoshi Ube
  • Kenichi Endo
    Kenichi Endo
    Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
    More by Kenichi Endo
  • Hiroyasu Sato
    Hiroyasu Sato
    Rigaku Corporation, 3-9-12 Matsubaracho, Akishima, Tokyo 196-8666, Japan
  • , and 
  • Mitsuhiko Shionoya*
    Mitsuhiko Shionoya
    Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
    *[email protected]
Cite this: J. Am. Chem. Soc. 2019, 141, 26, 10384–10389
Publication Date (Web):June 12, 2019
https://doi.org/10.1021/jacs.9b04123
Copyright © 2019 American Chemical Society

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    Abstract

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    Hetero-multinuclear metal complexes are a promising class of compounds applicable to photoluminescence, magnetism, and catalysis. In this work, we have developed a synthetic method for hetero-tetranuclear metal complexes by combining advantages of site-selective redox switching and transmetalation. First, a homo-tetranuclear CoII4 complex was converted to a mixed-valence CoIIICoII3 complex by site-selective oxidation, which was then transmetalated from CoII to NiII to form a heterometallic CoIIINiII3 complex. Finally, a CoIINiII3 complex was synthesized by metal-selective reduction on the CoIII site. The basic structural frameworks of the main products in the whole process starting from the CoII4 complex are isostructural. Notably, the CoIINiII3 complex was not accessible by direct mixing of ligand, CoII, and NiII. This method would provide an alternative strategy for highly selective synthesis of hetero-multinuclear metal complexes.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.9b04123.

    • Experimental procedures, characterization of compounds, NMR spectra, ESI mass spectra, UV–vis spectra, an XPS spectrum, crystallographic data, experimental details of the structural refinement, and stability constant calculation (PDF)

    • Single-crystal X-ray diffraction data for 1-CoII4 (CIF)

    • Single-crystal X-ray diffraction data for 2-CoIIICoII3 (CIF)

    • Single-crystal X-ray diffraction data for 3-CoIIINiII3 (CIF)

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    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

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