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

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

doi:10.1002/chem.201804898

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

Journal Article · Fri Sep 28 00:00:00 EDT 2018 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.201804898· OSTI ID:1490878

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)

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).

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1490878

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 68 Vol. 24; ISSN 0947-6539

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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

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