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

doi:10.1002/chem.201804898

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

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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:

Karmalkar, Deepika G. ^[1]; Li, Xiao ‐Xi ^[1]; Seo, Mi Sook ^[1]; Sankaralingam, Muniyandi ^[1]; Ohta, Takehiro ^[2]; Sarangi, Ritimukta ^[3];

^[4];

^[1]

Ewha Womans Univ., Seoul (Korea)
Univ. of Hyogo, Hyogo (Japan)
Stanford Univ., Stanford, CA (United States)
Sookmyung Women's Univ., Seoul (Korea)

Publication Date:: 2018-09-28

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:: 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.

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                    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.

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                    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.

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@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},

  number       = 68,

  volume       = 24,

  place        = {United States},

  year         = {2018},

  month        = {9}

}

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