A High‐Valent Manganese(IV)–Oxo–Cerium(IV) Complex and Its Enhanced Oxidizing Reactivity. Issue 45 (24th September 2019)

• Record Type: Journal Article
• Authors: Karmalkar, Deepika G.; Sankaralingam, Muniyandi; Seo, Mi Sook; Ezhov, Roman; Lee, Yong‐Min; Pushkar, Yulia N.; Kim, Won‐Suk; Fukuzumi, Shunichi; Nam, Wonwoo
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 45(2019)
• Page Start: 16124
• Page End: 16129
• Publication Date: 2019-09-24
• Subjects: biomimetic chemistry -- electron transfer -- high-valent manganese–oxo -- oxygen atom transfer -- redox-active metal ions; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201910032
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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. Abstract : A mononuclear nonheme manganese(IV)–oxo complex binding the Ce 4+ ion, [(dpaq)Mn IV (O)] + –Ce 4+, was synthesized and characterized. It has a Mn−O bond distance of 1.69 Å with a Raman band at 675 cm −1 . Electron transfer (ET) and oxygen atom transfer (OAT) reactivities of the [(dpaq)Mn IV (O)] + ‐Ce 4+ complex were found to be greater than those of Mn IV (O) complexes binding redox‐inactive metal ions, such as Ca 2+ and Sc 3+ .