A High-Valent Manganese(IV)–Oxo–Cerium(IV) Complex and Its Enhanced Oxidizing Reactivity

Deepika G. Karmalkar, Muniyandi Sankaralingam, Mi Sook Seo, Roman Ezhov, Yong Min Lee, Yulia N. Pushkar, Won Suk Kim, Shunichi Fukuzumi, Wonwoo Nam

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35 Scopus citations


A mononuclear nonheme manganese(IV)–oxo complex binding the Ce4+ ion, [(dpaq)MnIV(O)]+–Ce4+ (1-Ce4+), was synthesized by reacting [(dpaq)MnIII(OH)]+ (2) with cerium ammonium nitrate (CAN). 1-Ce4+ was characterized using various spectroscopic techniques, such as UV/Vis, EPR, CSI-MS, resonance Raman, XANES, and EXAFS, showing an Mn−O bond distance of 1.69 Å with a resonance Raman band at 675 cm−1. Electron-transfer and oxygen atom transfer reactivities of 1-Ce4+ were found to be greater than those of MnIV(O) intermediates binding redox-inactive metal ions (1-Mn+). This study reports the first example of a redox-active Ce4+ ion-bound MnIV-oxo complex and its spectroscopic characterization and chemical properties.

Original languageEnglish
Pages (from-to)16124-16129
Number of pages6
JournalAngewandte Chemie - International Edition
Issue number45
StatePublished - 4 Nov 2019

Bibliographical note

Funding Information:
This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), GRL (NRF-2010-00353 to W.N.), and Basic Science Research Program (2017R1D1A1B03029982 to Y.-M.L. and 2017R1D1A1B03032615 to S.F.), and a Grant-in-Aid (no. 16H02268 to S.F.) from MEXT, Japan. This research was also supported by NSF, CHE-1900476 (Y.N.P.). The use of the Advanced Photon Source, an Office of Science User Facility operated by the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract DE-AC02-06CH11357. The PNC/XSD (Sector 20) facilities at the Advanced Photon Source and research at these facilities were supported by the U.S. Department of Energy, Basic Energy Science and the Canadian Light Source. W.N. acknowledges the use of resonance Raman facility at IBS (IBS-R10-A1) in Korea.

Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


  • biomimetic chemistry
  • electron transfer
  • high-valent manganese–oxo
  • oxygen atom transfer
  • redox-active metal ions


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