一氧化碳与甲硅烷基锂和硅烯基锂的反应——首个稳定的四甲硅烷基双二酮基双自由基和1-硅代烯醇锂的合成与分离
The Reactions of Carbon Monoxide with Silyl and Silenyl Lithium - Synthesis and Isolation of the First Stable Tetra-Silyl Di-Ketyl Biradical and 1-Silaallenolate Lithium.
作者信息
Kratish Yosi, Pinchuk Daniel, Kaushansky Alexander, Molev Victoria, Tumanskii Boris, Bravo-Zhivotovskii Dmitry, Apeloig Yitzhak
机构信息
Schulich Faculty of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa, 32000, Israel.
出版信息
Angew Chem Int Ed Engl. 2019 Dec 19;58(52):18849-18853. doi: 10.1002/anie.201910336. Epub 2019 Nov 6.
Reactions of carbon monoxide (CO) with tBu MeSiLi and (E)-(tBu MeSi)(tBuMe Si)C=Si(SiMetBu )Li⋅2 THF (4) were studied both experimentally and computationally. Reaction of tBu MeSiLi with CO in hexane yields the first stable tetra-silyl di-ketyl biradical [(tBu MeSi) COLi] (3). Reaction of 4 with CO yields selectively and quantitatively the first reported 1-silaallenolate, (tBu MeSi)(tBuMe Si)C=C=Si(SiMetBu )OLi⋅THF (5). Both 3 and 5 were characterized by X-ray crystallography and biradical 3 also by EPR spectroscopy. Silaallenolate 5 reacts with Me SiCl to produce siloxy substituted 1-silaallene (tBu MeSi)(tBuMe Si)C=C=Si(SiMetBu )OSiMe . The reaction of 4 with CO provides a new route to 1-silaallenes. The mechanisms of the reactions of tBuMe SiLi and of 4 with CO were studied by DFT calculations.
对一氧化碳（CO）与叔丁基甲基硅基锂（tBu MeSiLi）以及（E）-（叔丁基甲基硅基）（叔丁基甲基硅基）C=Si（硅甲基叔丁基）锂·2THF（4）的反应进行了实验和计算研究。叔丁基甲基硅基锂在己烷中与CO反应生成首个稳定的四硅基二酮基双自由基[（叔丁基甲基硅基）₂COL i]（3）。4与CO反应选择性地定量生成首个报道的1-硅代烯醇盐，即（叔丁基甲基硅基）（叔丁基甲基硅基）C=C=Si（硅甲基叔丁基）OLi·THF（5）。3和5均通过X射线晶体学表征，双自由基3还通过电子顺磁共振光谱表征。硅代烯醇盐5与Me₂SiCl反应生成硅氧基取代的1-硅代丙二烯（叔丁基甲基硅基）（叔丁基甲基硅基）C=C=Si（硅甲基叔丁基）OSiMe₂。4与CO的反应为合成1-硅代丙二烯提供了一条新途径。通过密度泛函理论（DFT）计算研究了叔丁基甲基硅基锂和4与CO反应的机理。
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