Synthesis, characterization and reactions of the Vinylbis(trimethylsilyl)silyl anion

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Journal of Organometallic Chemistry Pub Date : 2025-02-24 DOI:10.1016/j.jorganchem.2025.123589

Eva M. Gulotty , Gregory D. Kortman , Nicole E. Proctor , Richard J. Staples , Shannon M. Biros , Matthias Bremer , William R. Winchester

{"title":"Synthesis, characterization and reactions of the Vinylbis(trimethylsilyl)silyl anion","authors":"Eva M. Gulotty , Gregory D. Kortman , Nicole E. Proctor , Richard J. Staples , Shannon M. Biros , Matthias Bremer , William R. Winchester","doi":"10.1016/j.jorganchem.2025.123589","DOIUrl":null,"url":null,"abstract":"<div><div>The delocalization of electrons across a vinylbis(trimethylsilyl)silyl anion has been studied with both lithium and potassium as counterions. The reaction of vinyl tris(trimethylsilyl)silane with potassium tert-butoxide forms the potassium salt while reaction with methyllithium produces the lithium salt, both by nucleophilic displacement of a trimethylsilyl group. The anion formed has been studied by 1H, 13C and 29Si NMR spectroscopy. A crystal structure of the 12-crown-4 complex of the lithium salt of the vinylbis(trimethylsilyl)silyl anion has been obtained. Reactions of the anion with acetic acid, Ph3SiCl, Ph2MeSiCl, PhCH2Cl and BrCH2CH2Br have been studied and the crystal structure of the product from reaction with Ph3SiCl is reported. Finally, we have studied the anion delocalization for these species using density functional theory and report the calculated rotational barrier for the vinyl silicon bond.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1031 ","pages":"Article 123589"},"PeriodicalIF":2.1000,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Organometallic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022328X2500083X","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}

引用次数: 0

Abstract

The delocalization of electrons across a vinylbis(trimethylsilyl)silyl anion has been studied with both lithium and potassium as counterions. The reaction of vinyl tris(trimethylsilyl)silane with potassium tert-butoxide forms the potassium salt while reaction with methyllithium produces the lithium salt, both by nucleophilic displacement of a trimethylsilyl group. The anion formed has been studied by ¹H, ¹³C and ²⁹Si NMR spectroscopy. A crystal structure of the 12-crown-4 complex of the lithium salt of the vinylbis(trimethylsilyl)silyl anion has been obtained. Reactions of the anion with acetic acid, Ph₃SiCl, Ph₂MeSiCl, PhCH₂Cl and BrCH₂CH₂Br have been studied and the crystal structure of the product from reaction with Ph₃SiCl is reported. Finally, we have studied the anion delocalization for these species using density functional theory and report the calculated rotational barrier for the vinyl silicon bond.

查看原文

微信好友朋友圈 QQ好友复制链接

本刊更多论文

乙烯基双（三甲基硅基）硅基阴离子的合成、表征及反应

用锂离子和钾离子作为反离子，研究了电子在乙烯基双（三甲基硅基）硅基阴离子上的离域。乙烯基三（三甲基硅基）硅烷与叔丁二氧化钾反应生成钾盐，与甲基锂反应生成锂盐，两者都是通过三甲基硅基的亲核位移生成锂盐。形成的阴离子通过1H、13C和29Si核磁共振谱进行了研究。得到了乙烯基双（三甲基硅基）硅基阴离子锂盐的12冠-4配合物的晶体结构。研究了该阴离子与乙酸、Ph3SiCl、Ph2MeSiCl、PhCH2Cl和BrCH2CH2Br的反应，并报道了与Ph3SiCl反应产物的晶体结构。最后，我们利用密度泛函理论研究了这些物种的阴离子离域，并报道了乙烯基硅键的计算旋转势垒。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文去求助

来源期刊

Journal of Organometallic Chemistry 化学-无机化学与核化学

CiteScore

4.40

自引率

8.70%

发文量

221

审稿时长

36 days

期刊介绍： The Journal of Organometallic Chemistry targets original papers dealing with theoretical aspects, structural chemistry, synthesis, physical and chemical properties (including reaction mechanisms), and practical applications of organometallic compounds. Organometallic compounds are defined as compounds that contain metal - carbon bonds. The term metal includes all alkali and alkaline earth metals, all transition metals and the lanthanides and actinides in the Periodic Table. Metalloids including the elements in Group 13 and the heavier members of the Groups 14 - 16 are also included. The term chemistry includes syntheses, characterizations and reaction chemistry of all such compounds. Research reports based on use of organometallic complexes in bioorganometallic chemistry, medicine, material sciences, homogeneous catalysis and energy conversion are also welcome. The scope of the journal has been enlarged to encompass important research on organometallic complexes in bioorganometallic chemistry and material sciences, and of heavier main group elements in organometallic chemistry. The journal also publishes review articles, short communications and notes.