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

Yosi Kratish; Daniel Pinchuk; Alexander Kaushansky; Victoria Molev; Boris Tumanskii; Dmitry Bravo-Zhivotovskii; Yitzhak Apeloig

doi:10.1002/anie.201910336

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

Yosi Kratish, Daniel Pinchuk, Alexander Kaushansky, Victoria Molev, Boris Tumanskii, Dmitry Bravo-Zhivotovskii, Yitzhak Apeloig

Technion - Israel Institute of Technology

Research output: Contribution to journal › Article › peer-review

Abstract

Reactions of carbon monoxide (CO) with tBu₂MeSiLi and (E)-(tBu₂MeSi)(tBuMe₂Si)C=Si(SiMetBu₂)Li⋅2 THF (4) were studied both experimentally and computationally. Reaction of tBu₂MeSiLi with CO in hexane yields the first stable tetra-silyl di-ketyl biradical [(tBu₂MeSi)₂COLi]^.₂ (3). Reaction of 4 with CO yields selectively and quantitatively the first reported 1-silaallenolate, (tBu₂MeSi)(tBuMe₂Si)C=C=Si(SiMetBu₂)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 (tBu₂MeSi)(tBuMe₂Si)C=C=Si(SiMetBu₂)OSiMe₃. The reaction of 4 with CO provides a new route to 1-silaallenes. The mechanisms of the reactions of tBuMe₂SiLi and of 4 with CO were studied by DFT calculations.

Original language	English
Pages (from-to)	18849-18853
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	52
DOIs	https://doi.org/10.1002/anie.201910336
State	Published - 19 Dec 2019

Keywords

1-silaallenolate
EPR
ketyl radicals
silenyl lithium
silyl lithium

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry

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10.1002/anie.201910336

Cite this

Kratish, Y., Pinchuk, D., Kaushansky, A., Molev, V., Tumanskii, B., Bravo-Zhivotovskii, D., & Apeloig, Y. (2019). 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. Angewandte Chemie - International Edition, 58(52), 18849-18853. https://doi.org/10.1002/anie.201910336

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title = "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",

abstract = "Reactions of carbon monoxide (CO) with tBu2MeSiLi and (E)-(tBu2MeSi)(tBuMe2Si)C=Si(SiMetBu2)Li⋅2 THF (4) were studied both experimentally and computationally. Reaction of tBu2MeSiLi with CO in hexane yields the first stable tetra-silyl di-ketyl biradical [(tBu2MeSi)2COLi].2 (3). Reaction of 4 with CO yields selectively and quantitatively the first reported 1-silaallenolate, (tBu2MeSi)(tBuMe2Si)C=C=Si(SiMetBu2)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 (tBu2MeSi)(tBuMe2Si)C=C=Si(SiMetBu2)OSiMe3. The reaction of 4 with CO provides a new route to 1-silaallenes. The mechanisms of the reactions of tBuMe2SiLi and of 4 with CO were studied by DFT calculations.",

keywords = "1-silaallenolate, EPR, ketyl radicals, silenyl lithium, silyl lithium",

author = "Yosi Kratish and Daniel Pinchuk and Alexander Kaushansky and Victoria Molev and Boris Tumanskii and Dmitry Bravo-Zhivotovskii and Yitzhak Apeloig",

note = "Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2019",

month = dec,

day = "19",

doi = "10.1002/anie.201910336",

language = "الإنجليزيّة",

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Kratish, Y, Pinchuk, D, Kaushansky, A, Molev, V, Tumanskii, B, Bravo-Zhivotovskii, D & Apeloig, Y 2019, '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', Angewandte Chemie - International Edition, vol. 58, no. 52, pp. 18849-18853. https://doi.org/10.1002/anie.201910336

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. / Kratish, Yosi; Pinchuk, Daniel; Kaushansky, Alexander et al.
In: Angewandte Chemie - International Edition, Vol. 58, No. 52, 19.12.2019, p. 18849-18853.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - 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

AU - Kratish, Yosi

AU - Pinchuk, Daniel

AU - Kaushansky, Alexander

AU - Molev, Victoria

AU - Tumanskii, Boris

AU - Bravo-Zhivotovskii, Dmitry

AU - Apeloig, Yitzhak

PY - 2019/12/19

Y1 - 2019/12/19

N2 - Reactions of carbon monoxide (CO) with tBu2MeSiLi and (E)-(tBu2MeSi)(tBuMe2Si)C=Si(SiMetBu2)Li⋅2 THF (4) were studied both experimentally and computationally. Reaction of tBu2MeSiLi with CO in hexane yields the first stable tetra-silyl di-ketyl biradical [(tBu2MeSi)2COLi].2 (3). Reaction of 4 with CO yields selectively and quantitatively the first reported 1-silaallenolate, (tBu2MeSi)(tBuMe2Si)C=C=Si(SiMetBu2)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 (tBu2MeSi)(tBuMe2Si)C=C=Si(SiMetBu2)OSiMe3. The reaction of 4 with CO provides a new route to 1-silaallenes. The mechanisms of the reactions of tBuMe2SiLi and of 4 with CO were studied by DFT calculations.

AB - Reactions of carbon monoxide (CO) with tBu2MeSiLi and (E)-(tBu2MeSi)(tBuMe2Si)C=Si(SiMetBu2)Li⋅2 THF (4) were studied both experimentally and computationally. Reaction of tBu2MeSiLi with CO in hexane yields the first stable tetra-silyl di-ketyl biradical [(tBu2MeSi)2COLi].2 (3). Reaction of 4 with CO yields selectively and quantitatively the first reported 1-silaallenolate, (tBu2MeSi)(tBuMe2Si)C=C=Si(SiMetBu2)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 (tBu2MeSi)(tBuMe2Si)C=C=Si(SiMetBu2)OSiMe3. The reaction of 4 with CO provides a new route to 1-silaallenes. The mechanisms of the reactions of tBuMe2SiLi and of 4 with CO were studied by DFT calculations.

KW - 1-silaallenolate

KW - EPR

KW - ketyl radicals

KW - silenyl lithium

KW - silyl lithium

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U2 - 10.1002/anie.201910336

DO - 10.1002/anie.201910336

M3 - مقالة

C2 - 31591792

SN - 1433-7851

VL - 58

SP - 18849

EP - 18853

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 52

ER -

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

Abstract

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