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

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. [ABSTRACT FROM AUTHOR]