A biomimetic model for the cysteine dioxygenase (CDO) was found to be also capable of selectively dioxygenating selenocysteamine, suggesting that the lack of reactivity found for the CDO in combinati....

Selective oxidation of styrene to desired products is essential and challenging. In this study, we elucidate a unique pathway for the selective oxidation of styrene to polystyrene peroxo species, catalyzed by the cobalt(III) tert-butylperoxo complex, [CoIII(OOtBu)(qpy)(NCCH3)]2+ (1), under ambient conditions. Mechanistic investigations, including the structural determination of the diperoxo complex, [CoIII(qpy)(OOCH(Ph)CH2OOtBu)(NCCH3)]2+ (2), by X-ray analysis and theoretical calculations reveal that the reaction begins with the nucleophilic addition of styrene to the CoIII–OOtBu moiety in 1. This step is followed by an addition with an O2 molecule, forming a diperoxyl radical (PhCOO•(H)CH2OOtBu), which subsequently rebounds with CoII(qpy) to yield 2. In the presence of excess O2, complex 2 can further react with additional styrene molecules, leading to the formation of cobalt(III) polystyrene peroxo species.

Adding HClO4 to [(BnTPEN)MnIII–OO]+ in MeOH generates a short-lived MnIII–OOH species, which converts to a putative MnV [[double bond, length as m-dash]] O species. The potent MnV [[double bond, lengt...

High valent iron-oxygen intermediates in water: Non-heme iron enzymes’ exceptional reactivity is attributed to accessing high-valent iron oxygen species. Inorganic models provide insights into enzyme....

Various metalloenzymes employ O2 for oxidative reactions, which is crucial in catalysis and biological processes involving high-valent metal–oxygen species. This study introduces novel high-valent Co(...