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

Research output: Contribution to journalArticlepeer-review

10 Scopus citations

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).

Original languageEnglish
Pages (from-to)17927-17931
Number of pages5
JournalChemistry - A European Journal
Volume24
Issue number68
DOIs
StatePublished - 5 Dec 2018

Keywords

  • C−H bond activation
  • manganese
  • olefin epoxidation
  • radicals
  • sulfoxidation

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