Yunzhou Chen, Huiying Song, Yiming Hao, Matthew Y. Lui, Wing-Leung Wong, William W. Y. Lam, Bun Chan*, Huatian Shi* and Wai-Lun Man*,
{"title":"Selective Aerobic Peroxidation of Styrene Catalyzed by a Cobalt tert-Butylperoxo Complex","authors":"Yunzhou Chen, Huiying Song, Yiming Hao, Matthew Y. Lui, Wing-Leung Wong, William W. Y. Lam, Bun Chan*, Huatian Shi* and Wai-Lun Man*, ","doi":"10.1021/jacsau.5c0013910.1021/jacsau.5c00139","DOIUrl":null,"url":null,"abstract":"<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 1090–1095"},"PeriodicalIF":8.5000,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00139","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"JACS Au","FirstCategoryId":"1085","ListUrlMain":"https://pubs.acs.org/doi/10.1021/jacsau.5c00139","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","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(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.