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. |