Shourya Gupta, Dhanusree C. Kakkarakkal, S. Chantal E. Stieber, Subrata Kundu
{"title":"CuCl2氧化苯酚的机理","authors":"Shourya Gupta, Dhanusree C. Kakkarakkal, S. Chantal E. Stieber, Subrata Kundu","doi":"10.1002/ejic.202500113","DOIUrl":null,"url":null,"abstract":"<p>Although copper-catalyzed organic transformations are prevalent, insights into the interactions of phenols with simple copper(II) salts are not well understood. In contrast, inspired by the oxygenase-type modifications of the phenolic substrates, the reactions of substituted phenols with metastable copper–oxygen intermediates are well documented. The present report sheds light on the reactions of substituted phenols with benchtop stable CuCl<sub>2</sub> salt and the role of a common base like triethylamine. Moreover, the reactions of substituted phenols with CuCl<sub>2</sub> in the presence of weakly coordinating tripodal <i>N</i>-nitrosated ligand <b>L</b><sup><b>3NO</b></sup> have been illustrated, while a closely related tripodal copper(II) complex <b>L</b><sup><b>3H</b></sup>CuCl<sub>2</sub> (<b>2</b>) of the corresponding non-nitrosated ligand <b>L</b><sup><b>3H</b></sup> does not react with the phenolic substrates. Phenol reactions with CuCl<sub>2</sub> in the presence of the <b>L</b><sup><b>3NO</b></sup> ligand enable in depth mechanistic investigation, thereby illustrating a bimolecular rate law with Δ<i>H</i><sup>‡</sup> = 15.13 kcal mol<sup>−1</sup>, Δ<i>S</i><sup>‡</sup> = −9.6 eu, and kinetic isotope effect <i>k</i><sub>2</sub>(ArOH)/<i>k</i><sub>2</sub>(ArOD) in the range of 1.35–1.43. Thus, these findings suggest that simple copper(II) salts like CuCl<sub>2</sub> are capable of facilitating a proton-coupled electron transfer (PCET) pathway.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 24","pages":""},"PeriodicalIF":2.0000,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Mechanism of Phenol Oxidation by CuCl2\",\"authors\":\"Shourya Gupta, Dhanusree C. Kakkarakkal, S. Chantal E. Stieber, Subrata Kundu\",\"doi\":\"10.1002/ejic.202500113\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Although copper-catalyzed organic transformations are prevalent, insights into the interactions of phenols with simple copper(II) salts are not well understood. In contrast, inspired by the oxygenase-type modifications of the phenolic substrates, the reactions of substituted phenols with metastable copper–oxygen intermediates are well documented. The present report sheds light on the reactions of substituted phenols with benchtop stable CuCl<sub>2</sub> salt and the role of a common base like triethylamine. Moreover, the reactions of substituted phenols with CuCl<sub>2</sub> in the presence of weakly coordinating tripodal <i>N</i>-nitrosated ligand <b>L</b><sup><b>3NO</b></sup> have been illustrated, while a closely related tripodal copper(II) complex <b>L</b><sup><b>3H</b></sup>CuCl<sub>2</sub> (<b>2</b>) of the corresponding non-nitrosated ligand <b>L</b><sup><b>3H</b></sup> does not react with the phenolic substrates. Phenol reactions with CuCl<sub>2</sub> in the presence of the <b>L</b><sup><b>3NO</b></sup> ligand enable in depth mechanistic investigation, thereby illustrating a bimolecular rate law with Δ<i>H</i><sup>‡</sup> = 15.13 kcal mol<sup>−1</sup>, Δ<i>S</i><sup>‡</sup> = −9.6 eu, and kinetic isotope effect <i>k</i><sub>2</sub>(ArOH)/<i>k</i><sub>2</sub>(ArOD) in the range of 1.35–1.43. Thus, these findings suggest that simple copper(II) salts like CuCl<sub>2</sub> are capable of facilitating a proton-coupled electron transfer (PCET) pathway.</p>\",\"PeriodicalId\":38,\"journal\":{\"name\":\"European Journal of Inorganic Chemistry\",\"volume\":\"28 24\",\"pages\":\"\"},\"PeriodicalIF\":2.0000,\"publicationDate\":\"2025-06-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"European Journal of Inorganic Chemistry\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejic.202500113\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"European Journal of Inorganic Chemistry","FirstCategoryId":"1","ListUrlMain":"https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejic.202500113","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Although copper-catalyzed organic transformations are prevalent, insights into the interactions of phenols with simple copper(II) salts are not well understood. In contrast, inspired by the oxygenase-type modifications of the phenolic substrates, the reactions of substituted phenols with metastable copper–oxygen intermediates are well documented. The present report sheds light on the reactions of substituted phenols with benchtop stable CuCl2 salt and the role of a common base like triethylamine. Moreover, the reactions of substituted phenols with CuCl2 in the presence of weakly coordinating tripodal N-nitrosated ligand L3NO have been illustrated, while a closely related tripodal copper(II) complex L3HCuCl2 (2) of the corresponding non-nitrosated ligand L3H does not react with the phenolic substrates. Phenol reactions with CuCl2 in the presence of the L3NO ligand enable in depth mechanistic investigation, thereby illustrating a bimolecular rate law with ΔH‡ = 15.13 kcal mol−1, ΔS‡ = −9.6 eu, and kinetic isotope effect k2(ArOH)/k2(ArOD) in the range of 1.35–1.43. Thus, these findings suggest that simple copper(II) salts like CuCl2 are capable of facilitating a proton-coupled electron transfer (PCET) pathway.
期刊介绍:
The European Journal of Inorganic Chemistry (2019 ISI Impact Factor: 2.529) publishes Full Papers, Communications, and Minireviews from the entire spectrum of inorganic, organometallic, bioinorganic, and solid-state chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies.
The following journals have been merged to form the two leading journals, European Journal of Inorganic Chemistry and European Journal of Organic Chemistry:
Chemische Berichte
Bulletin des Sociétés Chimiques Belges
Bulletin de la Société Chimique de France
Gazzetta Chimica Italiana
Recueil des Travaux Chimiques des Pays-Bas
Anales de Química
Chimika Chronika
Revista Portuguesa de Química
ACH—Models in Chemistry
Polish Journal of Chemistry
The European Journal of Inorganic Chemistry continues to keep you up-to-date with important inorganic chemistry research results.