Aerobic Oxidation Reactivity of Well-Defined Cobalt(II) and Cobalt(III) Aminophenol Complexes.

ABSTRACT: This paper describes the synthesis and reactivity studies of three cobalt complexes bearing aminophenol-derived ligands without nitrogen substitution: Co^II(^tBu2APH)₂(^tBu2AP)₂ (1), Co^III₂(^tBu2APH)₂(^tBu2AP)₂(μ-^tBu2BAP)₂ (2), and Co^III(^tBu2AP)₃ (3), where ^tBu2APH = 2-amino-4,6-di-tert-butylphenol, ^tBu2AP = 2-amino-4,6-di-tert-butylphenolate, and μ-^tBu2BAP = bridging 2-amido-4,6-di-tert-butylphenolate. Stoichiometric reactivity studies of these well-defined complexes demonstrate the catalytic competency of both cobalt(II) and cobalt(III) complexes in the aerobic oxidative cyclization of ^tBu2APH with tert-butylisonitrile. Reactions with O₂ reveal the aerobic oxidation of the cobalt(II) complex 1 to generate the cobalt(III) species 2 and 3. UV-visible time-course studies and electron paramagnetic resonance spectroscopy indicate that this oxidation proceeds through a ligand-based radical intermediate. These studies represent the first example of well-defined cobalt aminophenol complexes that participate in catalytic aerobic oxidation reactions and highlight a key role for a ligand radical in the oxidation sequence.

SUBMITTER: Liu J 

PROVIDER: S-EPMC9328405 | biostudies-literature | 2022 Apr

REPOSITORIES: biostudies-literature