Unique σ-bond metathesis of silylalkynes promoted by an ansa-dimethylsilyl and oxo-bridged uranium metallocene

Jiaxi Wang; Ylia Gurevich; Mark Botoshansky; Moris S. Eisen

doi:10.1021/ja063443x

Unique σ-bond metathesis of silylalkynes promoted by an ansa-dimethylsilyl and oxo-bridged uranium metallocene

Jiaxi Wang, Ylia Gurevich, Mark Botoshansky, Moris S. Eisen^*

^*Corresponding author for this work

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

35 Scopus citations

Abstract

The tetrachloride salt of uranium reacts with 1 equiv of the lithium ligand Li₂[(C₅Me₄)₂SiMe₂] in DME to form the complex [η⁵-(C₅Me₄)₂SiMe₂]UCl₂·2LiCl·2DME (1), which undergoes a rapid hydrolysis in toluene to yield the dimeric bridged monochloride, monooxide complex [{[η⁵-(C₅Me₄)₂SiMe₂]UCl}₂(μ-O)(μ-Cl)•Li•1/2DME]₂ (2). Metathesis of 2 with BuLi in DME gives the mono-bridged dibutyl complex {[η⁵-(C₅Me₄)₂SiMe₂]UBu}₂(μ-O) (3). Complex 2 was characterized by solid-state X-ray analysis. Complex 3 was found to be an active catalyst for the disproportionation metathesis of TMSC≡CH (TMS = SiMe₃) and the cross-metathesis of TMSC≡CH or TMSC≡CTMS with various terminal alkynes. The metathesis of TMSC≡CH gives TMSC≡CTMS and HC≡CH, whereas the cross-metathesis of TMSC≡CH or TMSC≡CTMS with terminal alkynes (RC≡CH) yields TMSC≡CTMS, TMSC≡CR, and HC≡CH. In addition, TMSC≡CCH₃ also was found to react with ^tBuC≡CH, yielding TMSC≡CBu^t and CH₃C≡CH. A plausible mechanism for the catalytic process is presented.

Original language	English
Pages (from-to)	9350-9351
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	128
Issue number	29
DOIs	https://doi.org/10.1021/ja063443x
State	Published - 26 Jul 2006
Externally published	Yes

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@article{77915d3399de433fb270c4b105496f3b,

title = "Unique σ-bond metathesis of silylalkynes promoted by an ansa-dimethylsilyl and oxo-bridged uranium metallocene",

abstract = "The tetrachloride salt of uranium reacts with 1 equiv of the lithium ligand Li2[(C5Me4)2SiMe2] in DME to form the complex [η5-(C5Me4)2SiMe2]UCl2·2LiCl·2DME (1), which undergoes a rapid hydrolysis in toluene to yield the dimeric bridged monochloride, monooxide complex [{[η5-(C5Me4)2SiMe2]UCl}2(μ-O)(μ-Cl)•Li•1/2DME]2 (2). Metathesis of 2 with BuLi in DME gives the mono-bridged dibutyl complex {[η5-(C5Me4)2SiMe2]UBu}2(μ-O) (3). Complex 2 was characterized by solid-state X-ray analysis. Complex 3 was found to be an active catalyst for the disproportionation metathesis of TMSC≡CH (TMS = SiMe3) and the cross-metathesis of TMSC≡CH or TMSC≡CTMS with various terminal alkynes. The metathesis of TMSC≡CH gives TMSC≡CTMS and HC≡CH, whereas the cross-metathesis of TMSC≡CH or TMSC≡CTMS with terminal alkynes (RC≡CH) yields TMSC≡CTMS, TMSC≡CR, and HC≡CH. In addition, TMSC≡CCH3 also was found to react with tBuC≡CH, yielding TMSC≡CBut and CH3C≡CH. A plausible mechanism for the catalytic process is presented.",

author = "Jiaxi Wang and Ylia Gurevich and Mark Botoshansky and Eisen, {Moris S.}",

year = "2006",

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AU - Wang, Jiaxi

AU - Gurevich, Ylia

AU - Botoshansky, Mark

AU - Eisen, Moris S.

PY - 2006/7/26

Y1 - 2006/7/26

N2 - The tetrachloride salt of uranium reacts with 1 equiv of the lithium ligand Li2[(C5Me4)2SiMe2] in DME to form the complex [η5-(C5Me4)2SiMe2]UCl2·2LiCl·2DME (1), which undergoes a rapid hydrolysis in toluene to yield the dimeric bridged monochloride, monooxide complex [{[η5-(C5Me4)2SiMe2]UCl}2(μ-O)(μ-Cl)•Li•1/2DME]2 (2). Metathesis of 2 with BuLi in DME gives the mono-bridged dibutyl complex {[η5-(C5Me4)2SiMe2]UBu}2(μ-O) (3). Complex 2 was characterized by solid-state X-ray analysis. Complex 3 was found to be an active catalyst for the disproportionation metathesis of TMSC≡CH (TMS = SiMe3) and the cross-metathesis of TMSC≡CH or TMSC≡CTMS with various terminal alkynes. The metathesis of TMSC≡CH gives TMSC≡CTMS and HC≡CH, whereas the cross-metathesis of TMSC≡CH or TMSC≡CTMS with terminal alkynes (RC≡CH) yields TMSC≡CTMS, TMSC≡CR, and HC≡CH. In addition, TMSC≡CCH3 also was found to react with tBuC≡CH, yielding TMSC≡CBut and CH3C≡CH. A plausible mechanism for the catalytic process is presented.

AB - The tetrachloride salt of uranium reacts with 1 equiv of the lithium ligand Li2[(C5Me4)2SiMe2] in DME to form the complex [η5-(C5Me4)2SiMe2]UCl2·2LiCl·2DME (1), which undergoes a rapid hydrolysis in toluene to yield the dimeric bridged monochloride, monooxide complex [{[η5-(C5Me4)2SiMe2]UCl}2(μ-O)(μ-Cl)•Li•1/2DME]2 (2). Metathesis of 2 with BuLi in DME gives the mono-bridged dibutyl complex {[η5-(C5Me4)2SiMe2]UBu}2(μ-O) (3). Complex 2 was characterized by solid-state X-ray analysis. Complex 3 was found to be an active catalyst for the disproportionation metathesis of TMSC≡CH (TMS = SiMe3) and the cross-metathesis of TMSC≡CH or TMSC≡CTMS with various terminal alkynes. The metathesis of TMSC≡CH gives TMSC≡CTMS and HC≡CH, whereas the cross-metathesis of TMSC≡CH or TMSC≡CTMS with terminal alkynes (RC≡CH) yields TMSC≡CTMS, TMSC≡CR, and HC≡CH. In addition, TMSC≡CCH3 also was found to react with tBuC≡CH, yielding TMSC≡CBut and CH3C≡CH. A plausible mechanism for the catalytic process is presented.

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U2 - 10.1021/ja063443x

DO - 10.1021/ja063443x

M3 - 文章

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AN - SCOPUS:33746380273

SN - 0002-7863

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SP - 9350

EP - 9351

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 29

ER -

Unique σ-bond metathesis of silylalkynes promoted by an ansa-dimethylsilyl and oxo-bridged uranium metallocene

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