Synthesis of silenyllithiums li(R′ 3Si)Si=C(SiR 3)(1-Ad) via transient silyne-silylidene intermediates

Lieby Zborovsky; Roman Dobrovetsky; Mark Botoshansky; Dmitry Bravo-Zhivotovskii; Yitzhak Apeloig

doi:10.1021/ja308777v

Synthesis of silenyllithiums li(R′ ₃Si)Si=C(SiR ₃)(1-Ad) via transient silyne-silylidene intermediates

Lieby Zborovsky, Roman Dobrovetsky, Mark Botoshansky, Dmitry Bravo-Zhivotovskii, Yitzhak Apeloig

Technion - Israel Institute of Technology

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

Abstract

The first two lithium silenides, Li(tBu ₂MeSi)Si=C(SiMetBu ₂)(1-Ad) (1) and Li(tBuMe ₂Si)Si=C(SiMetBu ₂)(1-Ad) (2) were prepared by THF addition to the corresponding lithium-silenolates, [(tBu ₂MeSi) ₂Si=C(OLi)(1-Ad)] ̇(R ₃SiLi) (3a: R ₃Si=tBu ₂MeSi, 3b: R ₃Si=tBuMe ₂Si). 1 and 2 were crystallized, and their structures were determined by X-ray crystallography. This process requires the presence of both coaggregated silyllithium (R ₃SiLi) (3a and 3b) and THF. Based on reaction products and DFT calculations, it is suggested that elimination of tBu ₂MeSiOLi from 3a (or 3b) produces first the corresponding silyne intermediate which rearranges to the corresponding silylidene, which is then trapped by R ₃SiLi giving 1 (or 2).

Original language	English
Pages (from-to)	18229-18232
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	134
Issue number	44
DOIs	https://doi.org/10.1021/ja308777v
State	Published - 7 Nov 2012

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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@article{a66e7a50087e4cb59f0b7808ef793392,

title = "Synthesis of silenyllithiums li(R′ 3Si)Si=C(SiR 3)(1-Ad) via transient silyne-silylidene intermediates",

abstract = "The first two lithium silenides, Li(tBu 2MeSi)Si=C(SiMetBu 2)(1-Ad) (1) and Li(tBuMe 2Si)Si=C(SiMetBu 2)(1-Ad) (2) were prepared by THF addition to the corresponding lithium-silenolates, [(tBu 2MeSi) 2Si=C(OLi)(1-Ad)]{\. }(R 3SiLi) (3a: R 3Si=tBu 2MeSi, 3b: R 3Si=tBuMe 2Si). 1 and 2 were crystallized, and their structures were determined by X-ray crystallography. This process requires the presence of both coaggregated silyllithium (R 3SiLi) (3a and 3b) and THF. Based on reaction products and DFT calculations, it is suggested that elimination of tBu 2MeSiOLi from 3a (or 3b) produces first the corresponding silyne intermediate which rearranges to the corresponding silylidene, which is then trapped by R 3SiLi giving 1 (or 2).",

author = "Lieby Zborovsky and Roman Dobrovetsky and Mark Botoshansky and Dmitry Bravo-Zhivotovskii and Yitzhak Apeloig",

year = "2012",

month = nov,

day = "7",

doi = "10.1021/ja308777v",

language = "الإنجليزيّة",

volume = "134",

pages = "18229--18232",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "44",

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TY - JOUR

T1 - Synthesis of silenyllithiums li(R′ 3Si)Si=C(SiR 3)(1-Ad) via transient silyne-silylidene intermediates

AU - Zborovsky, Lieby

AU - Dobrovetsky, Roman

AU - Botoshansky, Mark

AU - Bravo-Zhivotovskii, Dmitry

AU - Apeloig, Yitzhak

PY - 2012/11/7

Y1 - 2012/11/7

N2 - The first two lithium silenides, Li(tBu 2MeSi)Si=C(SiMetBu 2)(1-Ad) (1) and Li(tBuMe 2Si)Si=C(SiMetBu 2)(1-Ad) (2) were prepared by THF addition to the corresponding lithium-silenolates, [(tBu 2MeSi) 2Si=C(OLi)(1-Ad)] ̇(R 3SiLi) (3a: R 3Si=tBu 2MeSi, 3b: R 3Si=tBuMe 2Si). 1 and 2 were crystallized, and their structures were determined by X-ray crystallography. This process requires the presence of both coaggregated silyllithium (R 3SiLi) (3a and 3b) and THF. Based on reaction products and DFT calculations, it is suggested that elimination of tBu 2MeSiOLi from 3a (or 3b) produces first the corresponding silyne intermediate which rearranges to the corresponding silylidene, which is then trapped by R 3SiLi giving 1 (or 2).

AB - The first two lithium silenides, Li(tBu 2MeSi)Si=C(SiMetBu 2)(1-Ad) (1) and Li(tBuMe 2Si)Si=C(SiMetBu 2)(1-Ad) (2) were prepared by THF addition to the corresponding lithium-silenolates, [(tBu 2MeSi) 2Si=C(OLi)(1-Ad)] ̇(R 3SiLi) (3a: R 3Si=tBu 2MeSi, 3b: R 3Si=tBuMe 2Si). 1 and 2 were crystallized, and their structures were determined by X-ray crystallography. This process requires the presence of both coaggregated silyllithium (R 3SiLi) (3a and 3b) and THF. Based on reaction products and DFT calculations, it is suggested that elimination of tBu 2MeSiOLi from 3a (or 3b) produces first the corresponding silyne intermediate which rearranges to the corresponding silylidene, which is then trapped by R 3SiLi giving 1 (or 2).

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U2 - 10.1021/ja308777v

DO - 10.1021/ja308777v

M3 - مقالة

C2 - 23088441

SN - 0002-7863

VL - 134

SP - 18229

EP - 18232

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 44

ER -

Synthesis of silenyllithiums li(R′ ₃Si)Si=C(SiR ₃)(1-Ad) via transient silyne-silylidene intermediates

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