A mononuclear nonheme manganese(IV)–oxo complex binding the Ce4+ion, [(dpaq)MnIV(O)]+–Ce4+(
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Abstract 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 of1 ‐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. -
Karmalkar, Deepika G. ; Sankaralingam, Muniyandi ; Seo, Mi Sook ; Ezhov, Roman ; Lee, Yong‐Min ; Pushkar, Yulia N. ; Kim, Won‐Suk ; Fukuzumi, Shunichi ; Nam, Wonwoo ( , Angewandte Chemie)