{"title":"Potassium Isopropyl(trimethylsilyl)amide and Potassium tert-Butyl(trimethylsilyl)amide: Solvent-Dependent Solution Structures and Reactivities","authors":"Jesse A. Spivey, and , David B. Collum*, ","doi":"10.1021/acs.organomet.5c0001310.1021/acs.organomet.5c00013","DOIUrl":null,"url":null,"abstract":"<p >Potassium isopropyl(trimethylsilyl)amide (KPTA) and potassium <i>tert</i>-butyl(trimethylsilyl)amide (KBTA) were prepared as stable 1.0 M stock solutions in Et<sub>3</sub>N or isolable crystalline solids. A combination of the method of continuous variations and a heavy reliance on <sup>29</sup>Si NMR spectroscopy revealed solvent-dependent dimers and monomers. DFT computations offered insights into the solvation. Weakly coordinating solvents such as toluene and triethylamine afford dimers. In THF, KPTA is dimeric, whereas KBTA is dimeric at low THF concentration and monomeric in neat THF. Chronic and often poorly understood loss of the <sup>29</sup>Si resonance made a broadly based, systematic study difficult and may have obscured deaggregation or ionization. Reactivity was probed using orthometallations by KBTA, which pressed the limits of its basicity and probably impacted the yields in some cases.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 5","pages":"684–690 684–690"},"PeriodicalIF":2.5000,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.organomet.5c00013","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
Potassium isopropyl(trimethylsilyl)amide (KPTA) and potassium tert-butyl(trimethylsilyl)amide (KBTA) were prepared as stable 1.0 M stock solutions in Et3N or isolable crystalline solids. A combination of the method of continuous variations and a heavy reliance on 29Si NMR spectroscopy revealed solvent-dependent dimers and monomers. DFT computations offered insights into the solvation. Weakly coordinating solvents such as toluene and triethylamine afford dimers. In THF, KPTA is dimeric, whereas KBTA is dimeric at low THF concentration and monomeric in neat THF. Chronic and often poorly understood loss of the 29Si resonance made a broadly based, systematic study difficult and may have obscured deaggregation or ionization. Reactivity was probed using orthometallations by KBTA, which pressed the limits of its basicity and probably impacted the yields in some cases.
期刊介绍：
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.
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