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), [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).
- Authors:
-
[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:
- 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.
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. https://doi.org/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. https://doi.org/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},
number = 68,
volume = 24,
place = {United States},
year = {2018},
month = {9}
}
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Figure1: UV/Vis spectral changes observed in the reaction of 1 (2.5 x 10-2mm, black line) and [RuIII(bpy)3]3+ (3.0 x 10-2mm) in CH3CN at -40°C. The peak at 450 nm was due to [RuII(bpy)3]2+. Inset shows the plot of the absorbance change at 620 nm due to 2 upon addition ofmore »
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Generation and Reactivity of a One‐Electron‐Oxidized Manganese(V) Imido Complex with a Tetraamido Macrocyclic Ligand
journal, August 2019
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