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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:
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},
number = 68,
volume = 24,
place = {United States},
year = {2018},
month = {9}
}

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