Mukesh Kumar Nayak , Rajat Rajiv Maharana , Anuradha Mohanty , Kousik Samanta , Sujit Roy
{"title":"钯锡杂二金属催化中 N-杂环碳烯的影响：对无保护吲哚的 C3-H 功能化的 DFT 支持研究","authors":"Mukesh Kumar Nayak , Rajat Rajiv Maharana , Anuradha Mohanty , Kousik Samanta , Sujit Roy","doi":"10.1039/d4cy00224e","DOIUrl":null,"url":null,"abstract":"<div><p>A new N-heterocyclic carbene (NHC)-based Pd–Sn heterobimetallic complex [(NHC)Pd(μ-Br)SnCl<sub>3</sub>]<sub>2</sub> with low steric crowding in the active catalytic region was designed. The reactivity of this complex was compared with a previously reported NHC–Pd–Sn complex (NHC)<sub>2</sub>PdBrSnCl<sub>3</sub> towards the C3–H functionalization of indoles with styrenes. The role of NHC in heterobimetallic catalysis was investigated in terms of the density functional theory by comparing the reactivity of these catalysts along with a cyclooctadiene (COD)-based Pd–Sn catalyst (COD)PdClSnCl<sub>3</sub>. Thermochemical calculations revealed that the catalytic cycle is thermodynamically favorable in the case of the NHC-based catalysts but not in the case of the COD-based one. An inverse kinetic isotope effect with a <em>k</em><sub>H</sub>/<em>k</em><sub>D</sub> of 0.44 was detected. This alludes to the migration of a hydride from the metal center to the carbon center being the rate-determining step of the reaction. Based on the experimental and computational findings, an appropriate mechanism is proposed.</p></div>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":null,"pages":null},"PeriodicalIF":5.4000,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Effect of N-heterocyclic carbene in palladium–tin heterobimetallic catalysis: a DFT supported study on the C3–H functionalization of unprotected indoles†\",\"authors\":\"Mukesh Kumar Nayak , Rajat Rajiv Maharana , Anuradha Mohanty , Kousik Samanta , Sujit Roy\",\"doi\":\"10.1039/d4cy00224e\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>A new N-heterocyclic carbene (NHC)-based Pd–Sn heterobimetallic complex [(NHC)Pd(μ-Br)SnCl<sub>3</sub>]<sub>2</sub> with low steric crowding in the active catalytic region was designed. The reactivity of this complex was compared with a previously reported NHC–Pd–Sn complex (NHC)<sub>2</sub>PdBrSnCl<sub>3</sub> towards the C3–H functionalization of indoles with styrenes. The role of NHC in heterobimetallic catalysis was investigated in terms of the density functional theory by comparing the reactivity of these catalysts along with a cyclooctadiene (COD)-based Pd–Sn catalyst (COD)PdClSnCl<sub>3</sub>. Thermochemical calculations revealed that the catalytic cycle is thermodynamically favorable in the case of the NHC-based catalysts but not in the case of the COD-based one. An inverse kinetic isotope effect with a <em>k</em><sub>H</sub>/<em>k</em><sub>D</sub> of 0.44 was detected. This alludes to the migration of a hydride from the metal center to the carbon center being the rate-determining step of the reaction. Based on the experimental and computational findings, an appropriate mechanism is proposed.</p></div>\",\"PeriodicalId\":4,\"journal\":{\"name\":\"ACS Applied Energy Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":5.4000,\"publicationDate\":\"2024-08-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Applied Energy Materials\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/org/science/article/pii/S2044475324003861\",\"RegionNum\":3,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Applied Energy Materials","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S2044475324003861","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Effect of N-heterocyclic carbene in palladium–tin heterobimetallic catalysis: a DFT supported study on the C3–H functionalization of unprotected indoles†
A new N-heterocyclic carbene (NHC)-based Pd–Sn heterobimetallic complex [(NHC)Pd(μ-Br)SnCl3]2 with low steric crowding in the active catalytic region was designed. The reactivity of this complex was compared with a previously reported NHC–Pd–Sn complex (NHC)2PdBrSnCl3 towards the C3–H functionalization of indoles with styrenes. The role of NHC in heterobimetallic catalysis was investigated in terms of the density functional theory by comparing the reactivity of these catalysts along with a cyclooctadiene (COD)-based Pd–Sn catalyst (COD)PdClSnCl3. Thermochemical calculations revealed that the catalytic cycle is thermodynamically favorable in the case of the NHC-based catalysts but not in the case of the COD-based one. An inverse kinetic isotope effect with a kH/kD of 0.44 was detected. This alludes to the migration of a hydride from the metal center to the carbon center being the rate-determining step of the reaction. Based on the experimental and computational findings, an appropriate mechanism is proposed.
期刊介绍：
ACS Applied Energy Materials is an interdisciplinary journal publishing original research covering all aspects of materials, engineering, chemistry, physics and biology relevant to energy conversion and storage. The journal is devoted to reports of new and original experimental and theoretical research of an applied nature that integrate knowledge in the areas of materials, engineering, physics, bioscience, and chemistry into important energy applications.
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