{"title":"一种基于 N-杂环碳烯的钯钳系统及其在氧化条件下的多功能反应性。","authors":"Haobin Li, Bo Zhang, Rui Feng and Shuai Guo","doi":"10.1039/D4DT00980K","DOIUrl":null,"url":null,"abstract":"<p >NHC-based pincers (NHC = N-heterocyclic carbene) have been broadly employed as supporting platforms, and their palladium complexes have found many synthetic applications. However, previous studies mainly focused on the NHC pincers of palladium featuring an oxidation number of +II. In contrast, oxidation of these well-defined Pd(<small>II</small>) species and the study of their fundamental high-valent Pd chemistry remain largely undeveloped. In addition, from a perspective of Pd<small><sup>II</sup></small>/Pd<small><sup>IV</sup></small> catalysis, the reactivity and degradation of NHC pincers in catalytically relevant reactions have not been well understood. In this work, a series of Pd(<small>II</small>) complexes supported by a well-known NHC^Aryl^NHC pincer platform have been prepared. Their reactivity towards various oxidizing reagents, including halogen surrogates, electrophilic fluorine reagents, and alkyl/aryl halides, has been examined. In some cases, ambient-characterizable high-valent Pd NHCs, which have been scarcely reported, were obtained. The carbenes incorporated into the pincer framework proved to be effective spectator donors. In contrast, the central aryl moiety exhibits versatile reactivity and collapse pathways, allowing it to function either as a spectator or a non-innocent actor.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":3.5000,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"An N-heterocyclic carbene-based pincer system of palladium and its versatile reactivity under oxidizing conditions†\",\"authors\":\"Haobin Li, Bo Zhang, Rui Feng and Shuai Guo\",\"doi\":\"10.1039/D4DT00980K\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >NHC-based pincers (NHC = N-heterocyclic carbene) have been broadly employed as supporting platforms, and their palladium complexes have found many synthetic applications. However, previous studies mainly focused on the NHC pincers of palladium featuring an oxidation number of +II. In contrast, oxidation of these well-defined Pd(<small>II</small>) species and the study of their fundamental high-valent Pd chemistry remain largely undeveloped. In addition, from a perspective of Pd<small><sup>II</sup></small>/Pd<small><sup>IV</sup></small> catalysis, the reactivity and degradation of NHC pincers in catalytically relevant reactions have not been well understood. In this work, a series of Pd(<small>II</small>) complexes supported by a well-known NHC^Aryl^NHC pincer platform have been prepared. Their reactivity towards various oxidizing reagents, including halogen surrogates, electrophilic fluorine reagents, and alkyl/aryl halides, has been examined. In some cases, ambient-characterizable high-valent Pd NHCs, which have been scarcely reported, were obtained. The carbenes incorporated into the pincer framework proved to be effective spectator donors. In contrast, the central aryl moiety exhibits versatile reactivity and collapse pathways, allowing it to function either as a spectator or a non-innocent actor.</p>\",\"PeriodicalId\":71,\"journal\":{\"name\":\"Dalton Transactions\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":3.5000,\"publicationDate\":\"2024-06-24\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Dalton Transactions\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/dt/d4dt00980k\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/dt/d4dt00980k","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
An N-heterocyclic carbene-based pincer system of palladium and its versatile reactivity under oxidizing conditions†
NHC-based pincers (NHC = N-heterocyclic carbene) have been broadly employed as supporting platforms, and their palladium complexes have found many synthetic applications. However, previous studies mainly focused on the NHC pincers of palladium featuring an oxidation number of +II. In contrast, oxidation of these well-defined Pd(II) species and the study of their fundamental high-valent Pd chemistry remain largely undeveloped. In addition, from a perspective of PdII/PdIV catalysis, the reactivity and degradation of NHC pincers in catalytically relevant reactions have not been well understood. In this work, a series of Pd(II) complexes supported by a well-known NHC^Aryl^NHC pincer platform have been prepared. Their reactivity towards various oxidizing reagents, including halogen surrogates, electrophilic fluorine reagents, and alkyl/aryl halides, has been examined. In some cases, ambient-characterizable high-valent Pd NHCs, which have been scarcely reported, were obtained. The carbenes incorporated into the pincer framework proved to be effective spectator donors. In contrast, the central aryl moiety exhibits versatile reactivity and collapse pathways, allowing it to function either as a spectator or a non-innocent actor.
期刊介绍:
Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.