{"title":"Efficient cyanosilylation of carbonyls using a well-defined dimeric sodium complex","authors":"","doi":"10.1016/j.jorganchem.2024.123350","DOIUrl":null,"url":null,"abstract":"<div><p>We present the synthesis and structural characterization of a novel dimeric sodium complex with the chemical composition [{Ph<sub>2</sub>Si(H)PhN}Na(THF)<sub>2</sub>]<sub>2</sub> (<strong>Na-1</strong>) supported by <em>N,1,1</em>-triphenylsilanamine fragment. The single-crystal X-ray diffraction analysis of complex <strong>Na-1</strong> in the solid state reveals the coordination of sodium ion with N and O atoms of the triphenylsilanamine unit, forming a four-membered ring. The sodium complex also demonstrates excellent activity as a pre-catalyst towards the cyanosilylation of a wide array of ketones with trimethylsilyl cyanide (TMSCN) to afford trimethylsilyloxypropanenitriles in excellent yield (up to 99 %) in a shorter time under mild and solvent-free reaction conditions and exhibits a greater tolerance to a variety of ketones bearing electron-withdrawing and electron-donating functional groups. The plausible mechanism of cyanosilylation of ketones catalyzed by the complex <strong>Na-1</strong> is also proposed.</p></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.1000,"publicationDate":"2024-09-02","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/S0022328X24003450","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
We present the synthesis and structural characterization of a novel dimeric sodium complex with the chemical composition [{Ph2Si(H)PhN}Na(THF)2]2 (Na-1) supported by N,1,1-triphenylsilanamine fragment. The single-crystal X-ray diffraction analysis of complex Na-1 in the solid state reveals the coordination of sodium ion with N and O atoms of the triphenylsilanamine unit, forming a four-membered ring. The sodium complex also demonstrates excellent activity as a pre-catalyst towards the cyanosilylation of a wide array of ketones with trimethylsilyl cyanide (TMSCN) to afford trimethylsilyloxypropanenitriles in excellent yield (up to 99 %) in a shorter time under mild and solvent-free reaction conditions and exhibits a greater tolerance to a variety of ketones bearing electron-withdrawing and electron-donating functional groups. The plausible mechanism of cyanosilylation of ketones catalyzed by the complex Na-1 is also proposed.
我们介绍了一种新型二聚钠络合物的合成和结构特征,该络合物的化学成分为[{Ph2Si(H)PhN}Na(THF)2]2(Na-1),由 N,1,1-三苯基硅胺片段支撑。络合物 Na-1 在固态下的单晶 X 射线衍射分析表明,钠离子与三苯基硅胺单元的 N 原子和 O 原子配位,形成了一个四元环。钠络合物作为一种前催化剂,在温和无溶剂的反应条件下,用三甲基硅基氰化物(TMSCN)对多种酮进行氰硅烷化反应,在较短的时间内获得三甲基硅氧基丙腈,收率极高(高达 99%)。此外,还提出了复合物 Na-1 催化酮的氰硅化反应的合理机理。
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.