A High-Valent Manganese(IV)-Oxo-Cerium(IV) Complex and Its Enhanced Oxidizing Reactivity

Deepika G Karmalkar; Muniyandi Sankaralingam; Mi Sook Seo; Roman Ezhov; Yong-Min Lee; Yulia N Pushkar; Won-Suk Kim; Shunichi Fukuzumi; Wonwoo Nam

doi:10.1002/anie.201910032

A High-Valent Manganese(IV)-Oxo-Cerium(IV) Complex and Its Enhanced Oxidizing Reactivity

Angew Chem Int Ed Engl. 2019 Nov 4;58(45):16124-16129. doi: 10.1002/anie.201910032. Epub 2019 Sep 24.

Authors

Affiliations

¹ Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 03760, Korea.
² Department of Physics and Astronomy, Purdue University, 525 Northwestern Ave., West Lafayette, IN, 47907, USA.
³ Faculty of Science and Engineering, Meijo University, Nagoya, Aichi, 468-0073, Japan.
⁴ School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, China.

PMID: 31489757
DOI: 10.1002/anie.201910032

Abstract

A mononuclear nonheme manganese(IV)-oxo complex binding the Ce⁴⁺ ion, [(dpaq)Mn^IV (O)]⁺ -Ce⁴⁺ (1-Ce⁴⁺ ), was synthesized by reacting [(dpaq)Mn^III (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 Mn^IV (O) intermediates binding redox-inactive metal ions (1-Mⁿ⁺ ). This study reports the first example of a redox-active Ce⁴⁺ ion-bound Mn^IV -oxo complex and its spectroscopic characterization and chemical properties.

Keywords: biomimetic chemistry; electron transfer; high-valent manganese-oxo; oxygen atom transfer; redox-active metal ions.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

Abstract

Publication types

Grants and funding