TY - JOUR
T1 - A High-Valent Manganese(IV)–Oxo–Cerium(IV) Complex and Its Enhanced Oxidizing Reactivity
AU - Karmalkar, Deepika G.
AU - Sankaralingam, Muniyandi
AU - Seo, Mi Sook
AU - Ezhov, Roman
AU - Lee, Yong Min
AU - Pushkar, Yulia N.
AU - Kim, Won Suk
AU - Fukuzumi, Shunichi
AU - Nam, Wonwoo
N1 - Funding Information:
This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), GRL (NRF-2010-00353 to W.N.), and Basic Science Research Program (2017R1D1A1B03029982 to Y.-M.L. and 2017R1D1A1B03032615 to S.F.), and a Grant-in-Aid (no. 16H02268 to S.F.) from MEXT, Japan. This research was also supported by NSF, CHE-1900476 (Y.N.P.). The use of the Advanced Photon Source, an Office of Science User Facility operated by the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract DE-AC02-06CH11357. The PNC/XSD (Sector 20) facilities at the Advanced Photon Source and research at these facilities were supported by the U.S. Department of Energy, Basic Energy Science and the Canadian Light Source. W.N. acknowledges the use of resonance Raman facility at IBS (IBS-R10-A1) in Korea.
Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2019/11/4
Y1 - 2019/11/4
N2 - 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.
AB - 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.
KW - biomimetic chemistry
KW - electron transfer
KW - high-valent manganese–oxo
KW - oxygen atom transfer
KW - redox-active metal ions
UR - http://www.scopus.com/inward/record.url?scp=85074026420&partnerID=8YFLogxK
U2 - 10.1002/anie.201910032
DO - 10.1002/anie.201910032
M3 - Article
C2 - 31489757
AN - SCOPUS:85074026420
SN - 1433-7851
VL - 58
SP - 16124
EP - 16129
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 45
ER -