skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: A Manganese(V)–Oxo Tetraamido Macrocyclic Ligand (TAML) Cation Radical Complex: Synthesis, Characterization, and Reactivity Studies

Abstract

Here, a mononuclear manganese(V)–oxo complex with tetraamido macrocyclic ligand (TAML), [Mn V(O)(TAML)] (1), is a sluggish oxidant in oxidation reactions. Herein, a mononuclear manganese(V)–oxo TAML cation radical complex, [Mn V(O)(TAML +.)] (2), is reported. It was synthesized by reacting [Mn III(TAML)] with 3.0 equivalents of [Ru III(bpy) 3] 3+ or upon addition of one–electron oxidant to 1 and then characterized thoroughly with various spectroscopic techniques along with DFT calculations. Although 1 is a sluggish oxidant, 2 is a strong oxidant capable of activating C–H bonds of hydrocarbons (i.e., hydrogen atom transfer reaction) and transferring its oxygen atom to thioanisoles and olefins (i.e., oxygen atom transfer reaction).

Authors:
 [1];  [1];  [1];  [1];  [2];  [3]; ORCiD logo [4]; ORCiD logo [1]
  1. Ewha Womans Univ., Seoul (Korea)
  2. Univ. of Hyogo, Hyogo (Japan)
  3. Stanford Univ., Stanford, CA (United States)
  4. Sookmyung Women's Univ., Seoul (Korea)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1490878
Grant/Contract Number:  
AC02-76SF00515; NRF-2012R1A3A2048842; NRF-2010-00353; NRF-2017R1C1B2002037; P41GM103393
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 24; Journal Issue: 68; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; C−H bond activation; manganese; olefin epoxidation; radicals; sulfoxidation

Citation Formats

Karmalkar, Deepika G., Li, Xiao ‐Xi, Seo, Mi Sook, Sankaralingam, Muniyandi, Ohta, Takehiro, Sarangi, Ritimukta, Hong, Seungwoo, and Nam, Wonwoo. A Manganese(V)–Oxo Tetraamido Macrocyclic Ligand (TAML) Cation Radical Complex: Synthesis, Characterization, and Reactivity Studies. United States: N. p., 2018. Web. doi:10.1002/chem.201804898.
Karmalkar, Deepika G., Li, Xiao ‐Xi, Seo, Mi Sook, Sankaralingam, Muniyandi, Ohta, Takehiro, Sarangi, Ritimukta, Hong, Seungwoo, & Nam, Wonwoo. A Manganese(V)–Oxo Tetraamido Macrocyclic Ligand (TAML) Cation Radical Complex: Synthesis, Characterization, and Reactivity Studies. United States. doi:10.1002/chem.201804898.
Karmalkar, Deepika G., Li, Xiao ‐Xi, Seo, Mi Sook, Sankaralingam, Muniyandi, Ohta, Takehiro, Sarangi, Ritimukta, Hong, Seungwoo, and Nam, Wonwoo. Fri . "A Manganese(V)–Oxo Tetraamido Macrocyclic Ligand (TAML) Cation Radical Complex: Synthesis, Characterization, and Reactivity Studies". United States. doi:10.1002/chem.201804898. https://www.osti.gov/servlets/purl/1490878.
@article{osti_1490878,
title = {A Manganese(V)–Oxo Tetraamido Macrocyclic Ligand (TAML) Cation Radical Complex: Synthesis, Characterization, and Reactivity Studies},
author = {Karmalkar, Deepika G. and Li, Xiao ‐Xi and Seo, Mi Sook and Sankaralingam, Muniyandi and Ohta, Takehiro and Sarangi, Ritimukta and Hong, Seungwoo and Nam, Wonwoo},
abstractNote = {Here, a mononuclear manganese(V)–oxo complex with tetraamido macrocyclic ligand (TAML), [MnV(O)(TAML)]– (1), is a sluggish oxidant in oxidation reactions. Herein, a mononuclear manganese(V)–oxo TAML cation radical complex, [MnV(O)(TAML+.)] (2), is reported. It was synthesized by reacting [MnIII(TAML)]– with 3.0 equivalents of [RuIII(bpy)3]3+ or upon addition of one–electron oxidant to 1 and then characterized thoroughly with various spectroscopic techniques along with DFT calculations. Although 1 is a sluggish oxidant, 2 is a strong oxidant capable of activating C–H bonds of hydrocarbons (i.e., hydrogen atom transfer reaction) and transferring its oxygen atom to thioanisoles and olefins (i.e., oxygen atom transfer reaction).},
doi = {10.1002/chem.201804898},
journal = {Chemistry - A European Journal},
issn = {0947-6539},
number = 68,
volume = 24,
place = {United States},
year = {2018},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Biological Water Oxidation
journal, March 2013

  • Cox, Nicholas; Pantazis, Dimitrios A.; Neese, Frank
  • Accounts of Chemical Research, Vol. 46, Issue 7
  • DOI: 10.1021/ar3003249

Zur möglichen Rolle des protonengekoppelten Elektronentransfers (PCET) bei der Oxidation von Wasser durch das Photosystem II
journal, July 2007

  • Meyer, Thomas J.; Huynh, My Hang V.; Thorp, H. Holden
  • Angewandte Chemie, Vol. 119, Issue 28
  • DOI: 10.1002/ange.200600917

Mn(V)(O) versus Cr(V)(O) Porphyrinoid Complexes: Structural Characterization and Implications for Basicity Controlling H-Atom Abstraction
journal, August 2015

  • Baglia, Regina A.; Prokop-Prigge, Katharine A.; Neu, Heather M.
  • Journal of the American Chemical Society, Vol. 137, Issue 34
  • DOI: 10.1021/jacs.5b05142

A Manganese(V)–Oxo Complex: Synthesis by Dioxygen Activation and Enhancement of Its Oxidizing Power by Binding Scandium Ion
journal, June 2016

  • Hong, Seungwoo; Lee, Yong-Min; Sankaralingam, Muniyandi
  • Journal of the American Chemical Society, Vol. 138, Issue 27
  • DOI: 10.1021/jacs.6b03874

A Mononuclear Nonheme Iron(V)-Imido Complex
journal, June 2017

  • Hong, Seungwoo; Sutherlin, Kyle D.; Vardhaman, Anil Kumar
  • Journal of the American Chemical Society, Vol. 139, Issue 26
  • DOI: 10.1021/jacs.7b04695

Heme Enzyme Structure and Function
journal, January 2014


Progress Toward a Molecular Mechanism of Water Oxidation in Photosystem II
journal, May 2017


Hydrocarbon Hydroxylation by Cytochrome P450 Enzymes
journal, February 2010

  • Ortiz de Montellano, Paul R.
  • Chemical Reviews, Vol. 110, Issue 2
  • DOI: 10.1021/cr9002193

Native structure of photosystem II at 1.95 Å resolution viewed by femtosecond X-ray pulses
journal, November 2014

  • Suga, Michihiro; Akita, Fusamichi; Hirata, Kunio
  • Nature, Vol. 517, Issue 7532
  • DOI: 10.1038/nature13991

Tuning Reactivity and Mechanism in Oxidation Reactions by Mononuclear Nonheme Iron(IV)-Oxo Complexes
journal, February 2014

  • Nam, Wonwoo; Lee, Yong-Min; Fukuzumi, Shunichi
  • Accounts of Chemical Research, Vol. 47, Issue 4
  • DOI: 10.1021/ar400258p

Oxygen-Atom Transfer Reactivity of Axially Ligated Mn(V)–Oxo Complexes: Evidence for Enhanced Electrophilic and Nucleophilic Pathways
journal, September 2014

  • Neu, Heather M.; Yang, Tzuhsiung; Baglia, Regina A.
  • Journal of the American Chemical Society, Vol. 136, Issue 39
  • DOI: 10.1021/ja507177h

Manganese Catalyzed C–H Halogenation
journal, May 2015


High-Valent Manganese–Oxo Valence Tautomers and the Influence of Lewis/Brönsted Acids on C–H Bond Cleavage
journal, September 2016


Iron(IV)hydroxide pKa and the Role of Thiolate Ligation in C-H Bond Activation by Cytochrome P450
journal, November 2013


Mechanisms of Sulfoxidation Catalyzed by High-Valent Intermediates of Heme Enzymes:  Electron-Transfer vs Oxygen-Transfer Mechanism
journal, October 1999

  • Goto, Yoshio; Matsui, Toshitaka; Ozaki, Shin-ichi
  • Journal of the American Chemical Society, Vol. 121, Issue 41
  • DOI: 10.1021/ja9901359

Strong Inhibition of O-Atom Transfer Reactivity for Mn IV (O)(π-Radical-Cation)(Lewis Acid) versus Mn V (O) Porphyrinoid Complexes
journal, May 2015

  • Zaragoza, Jan Paulo T.; Baglia, Regina A.; Siegler, Maxime A.
  • Journal of the American Chemical Society, Vol. 137, Issue 20
  • DOI: 10.1021/jacs.5b00875

Toward the Synthesis of More Reactive S = 2 Non-Heme Oxoiron(IV) Complexes
journal, July 2015


Recent developments in manganese corrole chemistry
journal, April 2013

  • Liu, Hai-Yang; Mahmood, Mian HR; Qiu, Sheng-Xiang (Samuel)
  • Coordination Chemistry Reviews, Vol. 257, Issue 7-8
  • DOI: 10.1016/j.ccr.2012.12.017

Molecular Designs for Controlling the Local Environments around Metal Ions
journal, July 2015


Crystal structure of oxygen-evolving photosystem II at a resolution of 1.9 Å
journal, April 2011

  • Umena, Yasufumi; Kawakami, Keisuke; Shen, Jian-Ren
  • Nature, Vol. 473, Issue 7345
  • DOI: 10.1038/nature09913

A Manganese(V)–Oxo π-Cation Radical Complex: Influence of One-Electron Oxidation on Oxygen-Atom Transfer
journal, October 2011

  • Prokop, Katharine A.; Neu, Heather M.; de Visser, Sam P.
  • Journal of the American Chemical Society, Vol. 133, Issue 40
  • DOI: 10.1021/ja2066237

Oxygen Activation and Radical Transformations in Heme Proteins and Metalloporphyrins
journal, December 2017


Electronic structure of the oxygen-evolving complex in photosystem II prior to O-O bond formation
journal, August 2014


High-valent first-row transition-metal complexes of tetraamido (4N) and diamidodialkoxido or diamidophenolato (2N/2O) ligands: Synthesis, structure, and magnetochemistry
journal, October 2008

  • Popescu, Delia-Laura; Chanda, Arani; Stadler, Matthew
  • Coordination Chemistry Reviews, Vol. 252, Issue 18-20
  • DOI: 10.1016/j.ccr.2007.11.006

Epoxidation Catalysis by a Manganese Corrole and Isolation of an Oxomanganese(V) Corrole
journal, November 2000


A new look at the role of thiolate ligation in cytochrome P450
journal, January 2017

  • Yosca, Timothy H.; Ledray, Aaron P.; Ngo, Joanna
  • JBIC Journal of Biological Inorganic Chemistry, Vol. 22, Issue 2-3
  • DOI: 10.1007/s00775-016-1430-3

Biomimetic Reactivity of Oxygen-Derived Manganese and Iron Porphyrinoid Complexes
journal, October 2017


Hydrogen Atom Transfer Reactions of Mononuclear Nonheme Metal–Oxygen Intermediates
journal, August 2018


High-valent metal-oxo intermediates in energy demanding processes: from dioxygen reduction to water splitting
journal, April 2015


Epoxidation Catalysis by a Manganese Corrole and Isolation of an Oxomanganese(V) Corrole
journal, November 2000


Cytochrome P450 Compound I: Capture, Characterization, and C-H Bond Activation Kinetics
journal, November 2010


The Possible Role of Proton-Coupled Electron Transfer (PCET) in Water Oxidation by Photosystem II
journal, July 2007

  • Meyer, Thomas J.; Huynh, My Hang V.; Thorp, H. Holden
  • Angewandte Chemie International Edition, Vol. 46, Issue 28
  • DOI: 10.1002/anie.200600917

Chemical Redox Agents for Organometallic Chemistry
journal, January 1996

  • Connelly, Neil G.; Geiger, William E.
  • Chemical Reviews, Vol. 96, Issue 2
  • DOI: 10.1021/cr940053x

A Balancing Act: Stability versus Reactivity of Mn(O) Complexes
journal, September 2015


High-spin Mn–oxo complexes and their relevance to the oxygen-evolving complex within photosystem II
journal, April 2015

  • Gupta, Rupal; Taguchi, Taketo; Lassalle-Kaiser, Benedikt
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 17
  • DOI: 10.1073/pnas.1422800112

Valence Tautomerization of High-Valent Manganese(V)-Oxo Corrole Induced by Protonation of the Oxo Ligand
journal, November 2015

  • Bougher, Curt J.; Liu, Shuo; Hicks, Scott D.
  • Journal of the American Chemical Society, Vol. 137, Issue 45
  • DOI: 10.1021/jacs.5b09759

Achieving One-Electron Oxidation of a Mononuclear Nonheme Iron(V)-Imido Complex
journal, October 2017

  • Hong, Seungwoo; Lu, Xiaoyan; Lee, Yong-Min
  • Journal of the American Chemical Society, Vol. 139, Issue 41
  • DOI: 10.1021/jacs.7b08161

Molecular Catalysts for Water Oxidation
journal, July 2015


Oxygen−Oxygen Bond Formation Pathways Promoted by Ruthenium Complexes
journal, December 2009

  • Romain, Sophie; Vigara, Laura; Llobet, Antoni
  • Accounts of Chemical Research, Vol. 42, Issue 12
  • DOI: 10.1021/ar900240w

    Works referencing / citing this record:

    Generation and Reactivity of a One‐Electron‐Oxidized Manganese(V) Imido Complex with a Tetraamido Macrocyclic Ligand
    journal, August 2019

    • Shi, Huatian; Xie, Jianhui; Lam, William W. Y.
    • Chemistry – A European Journal, Vol. 25, Issue 56
    • DOI: 10.1002/chem.201902405