期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 58, 期 52, 页码 18849-18853出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201910336
关键词
1-silaallenolate; EPR; ketyl radicals; silenyl lithium; silyl lithium
资金
- Israel Science Foundation (ISF)
- Alexander Goldberg research fund at the Technion
- Minerva Foundation in Munich
- Ministry of Immigrant Absorption, State of Israel
Reactions of carbon monoxide (CO) with tBu(2)MeSiLi and (E)-(tBu(2)MeSi)(tBuMe(2)Si)C=Si(SiMetBu(2))Li.2 THF (4) were studied both experimentally and computationally. Reaction of tBu(2)MeSiLi with CO in hexane yields the first stable tetra-silyl di-ketyl biradical [(tBu(2)MeSi)(2)COLi](.)(2) (3). Reaction of 4 with CO yields selectively and quantitatively the first reported 1-silaallenolate, (tBu(2)MeSi)(tBuMe(2)Si)C=C=Si(SiMetBu(2))OLi.THF (5). Both 3 and 5 were characterized by X-ray crystallography and biradical 3 also by EPR spectroscopy. Silaallenolate 5 reacts with Me3SiCl to produce siloxy substituted 1-silaallene (tBu(2)MeSi)(tBuMe(2)Si)C=C=Si(SiMetBu(2))OSiMe3. The reaction of 4 with CO provides a new route to 1-silaallenes. The mechanisms of the reactions of tBuMe(2)SiLi and of 4 with CO were studied by DFT calculations.
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