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 DOI:10.1021/jacsau.5c0013910.1021/jacsau.5c00139

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

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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.

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钴叔丁基过氧配合物催化苯乙烯选择性好氧过氧化反应

苯乙烯的选择性氧化是必要的和具有挑战性的。在这项研究中，我们阐明了在环境条件下，由钴（III）叔丁基过氧配合物[CoIII(OOtBu)(qpy)(NCCH3)]2+(1)催化的苯乙烯选择性氧化成聚苯乙烯过氧物质的独特途径。机理研究，包括对二过氧配合物[CoIII(qpy)(OOCH(Ph)CH2OOtBu)(NCCH3)]2+(2)的结构测定，通过x射线分析和理论计算表明，该反应始于苯乙烯在1中的CoIII - ootbu部分的亲核加成。这一步之后，与一个O2分子加成，形成一个二过氧自由基（PhCOO•(H)CH2OOtBu），随后与CoII（qpy）反弹生成2。在过量O2存在的情况下，配合物2可以进一步与额外的苯乙烯分子反应，导致形成钴（III）聚苯乙烯过氧物质。

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