利用可回收离子液体催化剂对氢硅烷进行电化学氧化脱氢以生成硅基:一种构建 Si-O/Si-Si 键的高效方法

IF 9.3 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Green Chemistry Pub Date : 2024-09-30 DOI:10.1039/d4gc02663b
Zhaoxin Wei , Ziren Chen , Fei Xue , Yuancheng Yue , Shaofeng Wu , Yonghong Zhang , Bin Wang , Yu Xia , Weiwei Jin , Chenjiang Liu
{"title":"利用可回收离子液体催化剂对氢硅烷进行电化学氧化脱氢以生成硅基:一种构建 Si-O/Si-Si 键的高效方法","authors":"Zhaoxin Wei ,&nbsp;Ziren Chen ,&nbsp;Fei Xue ,&nbsp;Yuancheng Yue ,&nbsp;Shaofeng Wu ,&nbsp;Yonghong Zhang ,&nbsp;Bin Wang ,&nbsp;Yu Xia ,&nbsp;Weiwei Jin ,&nbsp;Chenjiang Liu","doi":"10.1039/d4gc02663b","DOIUrl":null,"url":null,"abstract":"<div><div>A highly efficient and sustainable approach was developed for the construction of Si–O/Si–Si bonds, through the electrochemical oxidative dehydrogenation of hydrosilanes with <em>O</em>-nucleophiles (<em>e.g.</em> phenols, naphthols, alcohols, and H<sub>2</sub>O) or hydrosilane self-condensation. The protocol employs a highly electrically conductive and recyclable ionic liquid as a catalyst, thus eliminating the need for external electrolytes and hydrogen atom transfer (HAT) agents. The ionic liquid could be easily recovered and reused for at least eight cycles with consistent performance. Notably, this electrochemical method exhibits a broad substrate scope and high functional-group compatibility (66 examples, up to 96% yield). Initial mechanistic studies show that silicon radicals are generated <em>via</em> the process of hydrogen atom transfer between bromine radicals and silanes, and KIE experiments demonstrate that Si–H bond cleavage is the rate-determining step of the reaction.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"26 19","pages":"Pages 10189-10195"},"PeriodicalIF":9.3000,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Electrochemical oxidative dehydrogenation of hydrosilanes to generate silyl radicals: an efficient method for the construction of Si–O/Si–Si bonds utilizing a recyclable ionic liquid catalyst†\",\"authors\":\"Zhaoxin Wei ,&nbsp;Ziren Chen ,&nbsp;Fei Xue ,&nbsp;Yuancheng Yue ,&nbsp;Shaofeng Wu ,&nbsp;Yonghong Zhang ,&nbsp;Bin Wang ,&nbsp;Yu Xia ,&nbsp;Weiwei Jin ,&nbsp;Chenjiang Liu\",\"doi\":\"10.1039/d4gc02663b\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>A highly efficient and sustainable approach was developed for the construction of Si–O/Si–Si bonds, through the electrochemical oxidative dehydrogenation of hydrosilanes with <em>O</em>-nucleophiles (<em>e.g.</em> phenols, naphthols, alcohols, and H<sub>2</sub>O) or hydrosilane self-condensation. The protocol employs a highly electrically conductive and recyclable ionic liquid as a catalyst, thus eliminating the need for external electrolytes and hydrogen atom transfer (HAT) agents. The ionic liquid could be easily recovered and reused for at least eight cycles with consistent performance. Notably, this electrochemical method exhibits a broad substrate scope and high functional-group compatibility (66 examples, up to 96% yield). Initial mechanistic studies show that silicon radicals are generated <em>via</em> the process of hydrogen atom transfer between bromine radicals and silanes, and KIE experiments demonstrate that Si–H bond cleavage is the rate-determining step of the reaction.</div></div>\",\"PeriodicalId\":78,\"journal\":{\"name\":\"Green Chemistry\",\"volume\":\"26 19\",\"pages\":\"Pages 10189-10195\"},\"PeriodicalIF\":9.3000,\"publicationDate\":\"2024-09-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Green Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/org/science/article/pii/S1463926224007672\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Green Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S1463926224007672","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0

摘要

通过氢硅烷与 O 型亲核物(如酚、萘酚、醇和 H2O)的电化学氧化脱氢反应或氢硅烷自缩合反应,开发出了一种构建 Si-O/Si-Si 键的高效、可持续方法。该方案采用高导电性和可回收的离子液体作为催化剂,因此无需外加电解质和氢原子转移(HAT)剂。离子液体可轻松回收并重复使用至少八个周期,且性能始终如一。值得注意的是,这种电化学方法具有广泛的底物范围和较高的官能团兼容性(66 个实例,收率高达 96%)。初步的机理研究表明,硅自由基是通过溴自由基和硅烷之间的氢原子转移过程产生的,KIE 实验证明,Si-H 键裂解是该反应的决定性步骤。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Electrochemical oxidative dehydrogenation of hydrosilanes to generate silyl radicals: an efficient method for the construction of Si–O/Si–Si bonds utilizing a recyclable ionic liquid catalyst†

Electrochemical oxidative dehydrogenation of hydrosilanes to generate silyl radicals: an efficient method for the construction of Si–O/Si–Si bonds utilizing a recyclable ionic liquid catalyst†

Electrochemical oxidative dehydrogenation of hydrosilanes to generate silyl radicals: an efficient method for the construction of Si–O/Si–Si bonds utilizing a recyclable ionic liquid catalyst†
A highly efficient and sustainable approach was developed for the construction of Si–O/Si–Si bonds, through the electrochemical oxidative dehydrogenation of hydrosilanes with O-nucleophiles (e.g. phenols, naphthols, alcohols, and H2O) or hydrosilane self-condensation. The protocol employs a highly electrically conductive and recyclable ionic liquid as a catalyst, thus eliminating the need for external electrolytes and hydrogen atom transfer (HAT) agents. The ionic liquid could be easily recovered and reused for at least eight cycles with consistent performance. Notably, this electrochemical method exhibits a broad substrate scope and high functional-group compatibility (66 examples, up to 96% yield). Initial mechanistic studies show that silicon radicals are generated via the process of hydrogen atom transfer between bromine radicals and silanes, and KIE experiments demonstrate that Si–H bond cleavage is the rate-determining step of the reaction.
求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
来源期刊
Green Chemistry
Green Chemistry 化学-化学综合
CiteScore
16.10
自引率
7.10%
发文量
677
审稿时长
1.4 months
期刊介绍: Green Chemistry is a journal that provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998), which defines green chemistry as the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry aims to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The journal welcomes submissions on all aspects of research relating to this endeavor and publishes original and significant cutting-edge research that is likely to be of wide general appeal. For a work to be published, it must present a significant advance in green chemistry, including a comparison with existing methods and a demonstration of advantages over those methods.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信