{"title":"硫代钯- sns配合物- Mizoroki-Heck交叉偶联催化剂","authors":"Saeed Ataie, Atousa Khanzadeh and R. Tom Baker","doi":"10.1039/D5DT01008J","DOIUrl":null,"url":null,"abstract":"<p >Phosphine-free catalysts for the Mizoroki–Heck cross-coupling reaction offer significant advantages in terms of air and moisture stability. We synthesized two palladium(<small>II</small>) complexes featuring a thiolate-imine-thioether SNS pincer ligand: Pd(κ<small><sup>2</sup></small>-SNS<small><sup>Me</sup></small>)<small><sub>2</sub></small> (<strong>Pd-1</strong>) and PdI(κ<small><sup>3</sup></small>-SNS<small><sup>Me</sup></small>) (<strong>Pd-2</strong>). Their catalytic activities were compared, with <strong>Pd-2</strong> demonstrating excellent reactivity at a low catalyst loading of 1.5 mol%, efficiently producing olefin products across various substrates within 5 hours. Conversely, <strong>Pd-1</strong> showed no catalytic activity due to its isomerization to a Pd(<small>II</small>)-N<small><sub>2</sub></small>S<small><sub>2</sub></small> complex <em>via</em> imine C–C bond formation at elevated temperatures, which restricted access to coordination sites necessary for oxidative addition and alkene coordination. Heating <strong>Pd-2</strong> with excess NEt<small><sub>3</sub></small> affords a Pd dithiolate tetramer, [Pd(μ-κ<small><sup>3</sup></small>-SNS)]<small><sub>4</sub></small><em>via</em> selective C–S bond activation.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 20","pages":" 8050-8054"},"PeriodicalIF":3.3000,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/dt/d5dt01008j?page=search","citationCount":"0","resultStr":"{\"title\":\"A palladium thiolate-SNS complex-catalyst for Mizoroki–Heck cross-coupling†\",\"authors\":\"Saeed Ataie, Atousa Khanzadeh and R. Tom Baker\",\"doi\":\"10.1039/D5DT01008J\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Phosphine-free catalysts for the Mizoroki–Heck cross-coupling reaction offer significant advantages in terms of air and moisture stability. We synthesized two palladium(<small>II</small>) complexes featuring a thiolate-imine-thioether SNS pincer ligand: Pd(κ<small><sup>2</sup></small>-SNS<small><sup>Me</sup></small>)<small><sub>2</sub></small> (<strong>Pd-1</strong>) and PdI(κ<small><sup>3</sup></small>-SNS<small><sup>Me</sup></small>) (<strong>Pd-2</strong>). Their catalytic activities were compared, with <strong>Pd-2</strong> demonstrating excellent reactivity at a low catalyst loading of 1.5 mol%, efficiently producing olefin products across various substrates within 5 hours. Conversely, <strong>Pd-1</strong> showed no catalytic activity due to its isomerization to a Pd(<small>II</small>)-N<small><sub>2</sub></small>S<small><sub>2</sub></small> complex <em>via</em> imine C–C bond formation at elevated temperatures, which restricted access to coordination sites necessary for oxidative addition and alkene coordination. Heating <strong>Pd-2</strong> with excess NEt<small><sub>3</sub></small> affords a Pd dithiolate tetramer, [Pd(μ-κ<small><sup>3</sup></small>-SNS)]<small><sub>4</sub></small><em>via</em> selective C–S bond activation.</p>\",\"PeriodicalId\":71,\"journal\":{\"name\":\"Dalton Transactions\",\"volume\":\" 20\",\"pages\":\" 8050-8054\"},\"PeriodicalIF\":3.3000,\"publicationDate\":\"2025-05-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.rsc.org/en/content/articlepdf/2025/dt/d5dt01008j?page=search\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Dalton Transactions\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2025/dt/d5dt01008j\",\"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/2025/dt/d5dt01008j","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
A palladium thiolate-SNS complex-catalyst for Mizoroki–Heck cross-coupling†
Phosphine-free catalysts for the Mizoroki–Heck cross-coupling reaction offer significant advantages in terms of air and moisture stability. We synthesized two palladium(II) complexes featuring a thiolate-imine-thioether SNS pincer ligand: Pd(κ2-SNSMe)2 (Pd-1) and PdI(κ3-SNSMe) (Pd-2). Their catalytic activities were compared, with Pd-2 demonstrating excellent reactivity at a low catalyst loading of 1.5 mol%, efficiently producing olefin products across various substrates within 5 hours. Conversely, Pd-1 showed no catalytic activity due to its isomerization to a Pd(II)-N2S2 complex via imine C–C bond formation at elevated temperatures, which restricted access to coordination sites necessary for oxidative addition and alkene coordination. Heating Pd-2 with excess NEt3 affords a Pd dithiolate tetramer, [Pd(μ-κ3-SNS)]4via selective C–S bond activation.
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.
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