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

Deepika G. Karmalkar; Xiao Xi Li; Mi Sook Seo; Muniyandi Sankaralingam; Takehiro Ohta; Ritimukta Sarangi; Seungwoo Hong; Wonwoo Nam

doi:10.1002/chem.201804898

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

Deepika G. Karmalkar, Xiao Xi Li, Mi Sook Seo, Muniyandi Sankaralingam, Takehiro Ohta, Ritimukta Sarangi, Seungwoo Hong, Wonwoo Nam

Department of Chemistry & Nanoscience

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

19 Scopus citations

Abstract

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).

Original language	English
Pages (from-to)	17927-17931
Number of pages	5
Journal	Chemistry - A European Journal
Volume	24
Issue number	68
DOIs	https://doi.org/10.1002/chem.201804898
State	Published - 5 Dec 2018

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Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

C−H bond activation
manganese
olefin epoxidation
radicals
sulfoxidation

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

abstract = "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).",

keywords = "C−H bond activation, manganese, olefin epoxidation, radicals, sulfoxidation",

author = "Karmalkar, {Deepika G.} and Li, {Xiao Xi} and Seo, {Mi Sook} and Muniyandi Sankaralingam and Takehiro Ohta and Ritimukta Sarangi and Seungwoo Hong and Wonwoo Nam",

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doi = "10.1002/chem.201804898",

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T1 - A Manganese(V)–Oxo Tetraamido Macrocyclic Ligand (TAML) Cation Radical Complex

T2 - Synthesis, Characterization, and Reactivity Studies

AU - Karmalkar, Deepika G.

AU - Li, Xiao Xi

AU - Seo, Mi Sook

AU - Sankaralingam, Muniyandi

AU - Ohta, Takehiro

AU - Sarangi, Ritimukta

AU - Hong, Seungwoo

AU - Nam, Wonwoo

PY - 2018/12/5

Y1 - 2018/12/5

N2 - 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).

AB - 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).

KW - C−H bond activation

KW - manganese

KW - olefin epoxidation

KW - radicals

KW - sulfoxidation

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DO - 10.1002/chem.201804898

M3 - Article

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AN - SCOPUS:85056708710

SN - 0947-6539

VL - 24

SP - 17927

EP - 17931

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 68

ER -

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

Abstract

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Keywords

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