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A Manganese(V)-Oxo Tetraamido Macrocyclic Ligand (TAML) Cation Radical Complex: Synthesis, Characterization, and Reactivity Studies
- Authors
- Karmalkar, Deepika G.; Li, Xiao-Xi; Seo, Mi Sook; Sankaralingam, Muniyandi; Ohta, Takehiro; Sarangi, Ritimukta; Hong, Seungwoo; Nam, Wonwoo
- Issue Date
- Dec-2018
- Publisher
- WILEY-V C H VERLAG GMBH
- Keywords
- C-H bond activation; manganese; olefin epoxidation; radicals; sulfoxidation
- Citation
- CHEMISTRY-A EUROPEAN JOURNAL, v.24, no.68, pp 17927 - 17931
- Pages
- 5
- Journal Title
- CHEMISTRY-A EUROPEAN JOURNAL
- Volume
- 24
- Number
- 68
- Start Page
- 17927
- End Page
- 17931
- ISSN
- 0947-6539
1521-3765
- 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).
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