Selective Aerobic Peroxidation of Styrene Catalyzed by a Cobalt tert-Butylperoxo Complex.

IF 8.5 Q1 CHEMISTRY, MULTIDISCIPLINARY
JACS Au Pub Date : 2025-02-28 eCollection Date: 2025-03-24 DOI:10.1021/jacsau.5c00139
Yunzhou Chen, Huiying Song, Yiming Hao, Matthew Y Lui, Wing-Leung Wong, William W Y Lam, Bun Chan, Huatian Shi, Wai-Lun Man
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引用次数: 0

Abstract

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(OO t Bu)(qpy)(NCCH3)]2+ (1), under ambient conditions. Mechanistic investigations, including the structural determination of the diperoxo complex, [CoIII(qpy)(OOCH(Ph)CH2OO t Bu)(NCCH3)]2+ (2), by X-ray analysis and theoretical calculations reveal that the reaction begins with the nucleophilic addition of styrene to the CoIII-OO t Bu 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.

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CiteScore
9.10
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