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A High‐Valent Manganese(IV)–Oxo–Cerium(IV) Complex and Its Enhanced Oxidizing Reactivity
Author(s) -
Karmalkar Deepika G.,
Sankaralingam Muniyandi,
Seo Mi Sook,
Ezhov Roman,
Lee YongMin,
Pushkar Yulia N.,
Kim WonSuk,
Fukuzumi Shunichi,
Nam Wonwoo
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201910032
Subject(s) - cerium , chemistry , manganese , redox , extended x ray absorption fine structure , electron paramagnetic resonance , inorganic chemistry , reactivity (psychology) , electron transfer , raman spectroscopy , oxidizing agent , ligand (biochemistry) , photochemistry , absorption spectroscopy , nuclear magnetic resonance , organic chemistry , medicine , biochemistry , physics , alternative medicine , receptor , quantum mechanics , pathology , optics
A mononuclear nonheme manganese(IV)–oxo complex binding the Ce 4+ ion, [(dpaq)Mn IV (O)] + –Ce 4+ ( 1 ‐Ce 4+ ), was synthesized by reacting [(dpaq)Mn III (OH)] + ( 2 ) with cerium ammonium nitrate (CAN). 1 ‐Ce 4+ 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 ‐Ce 4+ were found to be greater than those of Mn IV (O) intermediates binding redox‐inactive metal ions ( 1 ‐M n + ). This study reports the first example of a redox‐active Ce 4+ ion‐bound Mn IV ‐oxo complex and its spectroscopic characterization and chemical properties.