Yunzhou Chen, Huiying Song, Yiming Hao, Matthew Y Lui, Wing-Leung Wong, William W Y Lam, Bun Chan, Huatian Shi, Wai-Lun Man
{"title":"Selective Aerobic Peroxidation of Styrene Catalyzed by a Cobalt <i>tert</i>-Butylperoxo Complex.","authors":"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","DOIUrl":null,"url":null,"abstract":"<p><p>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) <i>tert</i>-butylperoxo complex, [Co<sup>III</sup>(OO <sup><i>t</i></sup> Bu)(qpy)(NCCH<sub>3</sub>)]<sup>2+</sup> (<b>1</b>), under ambient conditions. Mechanistic investigations, including the structural determination of the diperoxo complex, [Co<sup>III</sup>(qpy)(OOCH(Ph)CH<sub>2</sub>OO <sup><i>t</i></sup> Bu)(NCCH<sub>3</sub>)]<sup>2+</sup> (<b>2</b>), by X-ray analysis and theoretical calculations reveal that the reaction begins with the nucleophilic addition of styrene to the Co<sup>III</sup>-OO <sup><i>t</i></sup> Bu moiety in <b>1</b>. This step is followed by an addition with an O<sub>2</sub> molecule, forming a diperoxyl radical (PhCOO<sup>•</sup>(H)CH<sub>2</sub>OO<sup>t</sup>Bu), which subsequently rebounds with Co<sup>II</sup>(qpy) to yield <b>2</b>. In the presence of excess O<sub>2</sub>, complex <b>2</b> can further react with additional styrene molecules, leading to the formation of cobalt(III) polystyrene peroxo species.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 3","pages":"1090-1095"},"PeriodicalIF":8.5000,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11938028/pdf/","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"JACS Au","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1021/jacsau.5c00139","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/3/24 0:00:00","PubModel":"eCollection","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
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.