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

Yunzhou Chen; Huiying Song; Yiming Hao; Matthew Y. Lui; Wing Leung Wong; William W.Y. Lam; Bun Chan; Huatian Shi; Wai Lun Man

doi:10.1021/jacsau.5c00139

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

Yunzhou Chen, Huiying Song, Yiming Hao, Matthew Y. Lui, Wing Leung Wong, William W.Y. Lam, Bun Chan^*, Huatian Shi^*, Wai Lun Man^*

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Letter › peer-review

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, [Co^III(OO^tBu)(qpy)(NCCH₃)]²⁺ (1), under ambient conditions. Mechanistic investigations, including the structural determination of the diperoxo complex, [Co^III(qpy)(OOCH(Ph)CH₂OO^tBu)(NCCH₃)]²⁺ (2), by X-ray analysis and theoretical calculations reveal that the reaction begins with the nucleophilic addition of styrene to the Co^III-OO^tBu moiety in 1. This step is followed by an addition with an O₂ molecule, forming a diperoxyl radical (PhCOO^•(H)CH₂OO^tBu), which subsequently rebounds with Co^II(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.

Original language	English
Pages (from-to)	1090–1095
Number of pages	6
Journal	JACS Au
Volume	5
Issue number	3
Early online date	28 Feb 2025
DOIs	https://doi.org/10.1021/jacsau.5c00139
Publication status	Published - 24 Mar 2025

User-Defined Keywords

aerobic peroxidation
alkylperoxo complex
Cobalt catalysis
mechanism
styrene oxidation

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10.1021/jacsau.5c00139

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title = "Selective Aerobic Peroxidation of Styrene Catalyzed by a Cobalt tert-Butylperoxo Complex",

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(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.",

keywords = "aerobic peroxidation, alkylperoxo complex, Cobalt catalysis, mechanism, styrene oxidation",

author = "Yunzhou Chen and Huiying Song and Yiming Hao and Lui, {Matthew Y.} and Wong, {Wing Leung} and Lam, {William W.Y.} and Bun Chan and Huatian Shi and Man, {Wai Lun}",

note = "Funding Information: This work was financially supported by the Research Grants Council of Hong Kong (HKBU 12300121), Hong Kong Baptist University (RC-OFSGT2/20-21/SCI/008), and National Natural Science Foundation of China (Grant No. 22303013). Publisher Copyright: {\textcopyright} 2025 The Authors. Published by American Chemical Society.",

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doi = "10.1021/jacsau.5c00139",

language = "English",

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TY - JOUR

T1 - Selective Aerobic Peroxidation of Styrene Catalyzed by a Cobalt tert-Butylperoxo Complex

AU - Chen, Yunzhou

AU - Song, Huiying

AU - Hao, Yiming

AU - Lui, Matthew Y.

AU - Wong, Wing Leung

AU - Lam, William W.Y.

AU - Chan, Bun

AU - Shi, Huatian

AU - Man, Wai Lun

N1 - Funding Information: This work was financially supported by the Research Grants Council of Hong Kong (HKBU 12300121), Hong Kong Baptist University (RC-OFSGT2/20-21/SCI/008), and National Natural Science Foundation of China (Grant No. 22303013). Publisher Copyright: © 2025 The Authors. Published by American Chemical Society.

PY - 2025/3/24

Y1 - 2025/3/24

N2 - 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.

AB - 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.

KW - aerobic peroxidation

KW - alkylperoxo complex

KW - Cobalt catalysis

KW - mechanism

KW - styrene oxidation

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U2 - 10.1021/jacsau.5c00139

DO - 10.1021/jacsau.5c00139

M3 - Letter

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SN - 2691-3704

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JO - JACS Au

JF - JACS Au

IS - 3

ER -

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

Abstract

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