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

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

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

42 Scopus citations

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.

Original language	English
Pages (from-to)	16124-16129
Number of pages	6
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	45
DOIs	https://doi.org/10.1002/anie.201910032
State	Published - 4 Nov 2019

Bibliographical note

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

Keywords

biomimetic chemistry
electron transfer
high-valent manganese–oxo
oxygen atom transfer
redox-active metal ions

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10.1002/anie.201910032

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title = "A High-Valent Manganese(IV)–Oxo–Cerium(IV) Complex and Its Enhanced Oxidizing Reactivity",

abstract = "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 {\AA} 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.",

keywords = "biomimetic chemistry, electron transfer, high-valent manganese–oxo, oxygen atom transfer, redox-active metal ions",

author = "Karmalkar, {Deepika G.} and Muniyandi Sankaralingam and Seo, {Mi Sook} and Roman Ezhov and Lee, {Yong Min} and Pushkar, {Yulia N.} and Kim, {Won Suk} and Shunichi Fukuzumi and Wonwoo Nam",

note = "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: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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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

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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.

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KW - oxygen atom transfer

KW - redox-active metal ions

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ER -

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

Abstract

Bibliographical note

Keywords

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