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

Research output: Contribution to journalArticlepeer-review

24 Scopus citations

Abstract

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
Volume58
Issue number45
DOIs
StatePublished - 4 Nov 2019

Keywords

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

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