A Manganese(V)–Oxo Tetraamido Macrocyclic Ligand (TAML) Cation Radical Complex: Synthesis, Characterization, and Reactivity Studies. Issue 68 (19th November 2018)

• Record Type: Journal Article
• Authors: Karmalkar, Deepika G.; Li, Xiao‐Xi; Seo, Mi Sook; Sankaralingam, Muniyandi; Ohta, Takehiro; Sarangi, Ritimukta; Hong, Seungwoo; Nam, Wonwoo
• Is Part Of: Chemistry. Volume 24:Issue 68(2018)
• Page Start: 17927
• Page End: 17931
• Publication Date: 2018-11-19
• Subjects: C−H bond activation -- manganese -- olefin epoxidation -- radicals -- sulfoxidation; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201804898
• Languages: English
• ISSNs: 0947-6539

Abstract

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 to1 and then characterized thoroughly with various spectroscopic techniques along with DFT calculations. Although1 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). Abstract : Cpd I versus Cpd II : A mononuclear manganese(V)–oxo TAML cation radical complex, [Mn V (O)(TAML +. )], was synthesized and characterized with various spectroscopic techniques along with DFT calculations. This Mn–oxo intermediate 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).