Silicon-Carbon bond cleavage reactions of Ansa tungstenocene compounds: The [Me2Si] bridge as a site for metallocene functionalization

Cary E. Zachmanoglou; Hyosun Lee; Ho Jang Seung; Keliang Pang; Gerard Parkin

doi:10.1073/pnas.0803089105

Silicon-Carbon bond cleavage reactions of Ansa tungstenocene compounds: The [Me₂Si] bridge as a site for metallocene functionalization

Cary E. Zachmanoglou
, Hyosun Lee
, Ho Jang Seung
, Keliang Pang
, Gerard Parkin

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

4 Scopus citations

Abstract

[Me₂Si(Cp^Me2)₂]W(H)Cl is obtained via reaction of WCl₆ with a mixture of [Me₂Si(Cp ^Me2)₂]Li₂ and NaBH₄, from which the dichloride [Me₂Si(Cp^Me2)₂]WCl₂ is obtained via treatment with CHCl₃. [Me₂Si(Cp ^Me2)₂]WCl₂ provides a means to access other ansa tungstenocene compounds, such as [Me₂Si(Cp^Me2) ₂]WH₂, [Me₂Si(Cp^Me2) ₂]WMe₂, and [Me₂Si(Cp^Me2) ₂]WCO. Of most interest, the reactions of [Me₂Si(Cp ^Me2)₂]W(H)Cl with organolithium reagents do not yield simple ansa tungstenocene derivatives. Specifically, the reactions of [Me ₂Si(Cp^Me2)₂]W(H)Cl with MeLi, BuⁿLi, or PhLi result in the formation of mixed-ring tungstenocene compounds resulting from C-Si cleavage and functionalization of the ansa bridge, namely (Cp ^Me2)(η⁵,κ¹-C₅H ₂Me₂SiMe₂CH₂)WH, (Cp ^Me2)[η⁵,κ¹-C₅H ₂Me₂Si(Me)(Buⁿ)CH₂]WH, and (Cp ^Me2)[η⁵,κ¹-C₅H ₂Me₂SiMe₂(C₆H₄]WH, respectively. In contrast to the C-Si cleavage achieved by MeLi, Bu ⁿLi, and PhLi, the ansa bridge of [Me₂Si(Cp ^Me2)₂]W(H)Cl is inert to Bu^tLi and the product obtained is the fulvene ("tuck-in") complex [Me₂Si(Cp ^Me2)(η⁶-C₅MeH₂CH₂)] WH derived from dehydrohalogenation.

Original language	English
Pages (from-to)	11060-11065
Number of pages	6
Journal	Proceedings of the National Academy of Sciences of the United States of America
Volume	105
Issue number	32
DOIs	https://doi.org/10.1073/pnas.0803089105
State	Published - 12 Aug 2008

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@article{765d389f602b450cbf0b4d604d1011b3,

title = "Silicon-Carbon bond cleavage reactions of Ansa tungstenocene compounds: The [Me2Si] bridge as a site for metallocene functionalization",

abstract = "[Me2Si(CpMe2)2]W(H)Cl is obtained via reaction of WCl6 with a mixture of [Me2Si(Cp Me2)2]Li2 and NaBH4, from which the dichloride [Me2Si(CpMe2)2]WCl2 is obtained via treatment with CHCl3. [Me2Si(Cp Me2)2]WCl2 provides a means to access other ansa tungstenocene compounds, such as [Me2Si(CpMe2) 2]WH2, [Me2Si(CpMe2) 2]WMe2, and [Me2Si(CpMe2) 2]WCO. Of most interest, the reactions of [Me2Si(Cp Me2)2]W(H)Cl with organolithium reagents do not yield simple ansa tungstenocene derivatives. Specifically, the reactions of [Me 2Si(CpMe2)2]W(H)Cl with MeLi, BunLi, or PhLi result in the formation of mixed-ring tungstenocene compounds resulting from C-Si cleavage and functionalization of the ansa bridge, namely (Cp Me2)(η5,κ1-C5H 2Me2SiMe2CH2)WH, (Cp Me2)[η5,κ1-C5H 2Me2Si(Me)(Bun)CH2]WH, and (Cp Me2)[η5,κ1-C5H 2Me2SiMe2(C6H4]WH, respectively. In contrast to the C-Si cleavage achieved by MeLi, Bu nLi, and PhLi, the ansa bridge of [Me2Si(Cp Me2)2]W(H)Cl is inert to ButLi and the product obtained is the fulvene ({"}tuck-in{"}) complex [Me2Si(Cp Me2)(η6-C5MeH2CH2)] WH derived from dehydrohalogenation.",

author = "Zachmanoglou, \{Cary E.\} and Hyosun Lee and Seung, \{Ho Jang\} and Keliang Pang and Gerard Parkin",

year = "2008",

month = aug,

day = "12",

doi = "10.1073/pnas.0803089105",

language = "English",

volume = "105",

pages = "11060--11065",

journal = "Proceedings of the National Academy of Sciences of the United States of America",

issn = "0027-8424",

publisher = "National Academy of Sciences",

number = "32",

}

Silicon-Carbon bond cleavage reactions of Ansa tungstenocene compounds: The [Me₂Si] bridge as a site for metallocene functionalization. / Zachmanoglou, Cary E.; Lee, Hyosun; Seung, Ho Jang et al.
In: Proceedings of the National Academy of Sciences of the United States of America, Vol. 105, No. 32, 12.08.2008, p. 11060-11065.

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

TY - JOUR

T1 - Silicon-Carbon bond cleavage reactions of Ansa tungstenocene compounds

T2 - The [Me2Si] bridge as a site for metallocene functionalization

AU - Zachmanoglou, Cary E.

AU - Lee, Hyosun

AU - Seung, Ho Jang

AU - Pang, Keliang

AU - Parkin, Gerard

PY - 2008/8/12

Y1 - 2008/8/12

N2 - [Me2Si(CpMe2)2]W(H)Cl is obtained via reaction of WCl6 with a mixture of [Me2Si(Cp Me2)2]Li2 and NaBH4, from which the dichloride [Me2Si(CpMe2)2]WCl2 is obtained via treatment with CHCl3. [Me2Si(Cp Me2)2]WCl2 provides a means to access other ansa tungstenocene compounds, such as [Me2Si(CpMe2) 2]WH2, [Me2Si(CpMe2) 2]WMe2, and [Me2Si(CpMe2) 2]WCO. Of most interest, the reactions of [Me2Si(Cp Me2)2]W(H)Cl with organolithium reagents do not yield simple ansa tungstenocene derivatives. Specifically, the reactions of [Me 2Si(CpMe2)2]W(H)Cl with MeLi, BunLi, or PhLi result in the formation of mixed-ring tungstenocene compounds resulting from C-Si cleavage and functionalization of the ansa bridge, namely (Cp Me2)(η5,κ1-C5H 2Me2SiMe2CH2)WH, (Cp Me2)[η5,κ1-C5H 2Me2Si(Me)(Bun)CH2]WH, and (Cp Me2)[η5,κ1-C5H 2Me2SiMe2(C6H4]WH, respectively. In contrast to the C-Si cleavage achieved by MeLi, Bu nLi, and PhLi, the ansa bridge of [Me2Si(Cp Me2)2]W(H)Cl is inert to ButLi and the product obtained is the fulvene ("tuck-in") complex [Me2Si(Cp Me2)(η6-C5MeH2CH2)] WH derived from dehydrohalogenation.

AB - [Me2Si(CpMe2)2]W(H)Cl is obtained via reaction of WCl6 with a mixture of [Me2Si(Cp Me2)2]Li2 and NaBH4, from which the dichloride [Me2Si(CpMe2)2]WCl2 is obtained via treatment with CHCl3. [Me2Si(Cp Me2)2]WCl2 provides a means to access other ansa tungstenocene compounds, such as [Me2Si(CpMe2) 2]WH2, [Me2Si(CpMe2) 2]WMe2, and [Me2Si(CpMe2) 2]WCO. Of most interest, the reactions of [Me2Si(Cp Me2)2]W(H)Cl with organolithium reagents do not yield simple ansa tungstenocene derivatives. Specifically, the reactions of [Me 2Si(CpMe2)2]W(H)Cl with MeLi, BunLi, or PhLi result in the formation of mixed-ring tungstenocene compounds resulting from C-Si cleavage and functionalization of the ansa bridge, namely (Cp Me2)(η5,κ1-C5H 2Me2SiMe2CH2)WH, (Cp Me2)[η5,κ1-C5H 2Me2Si(Me)(Bun)CH2]WH, and (Cp Me2)[η5,κ1-C5H 2Me2SiMe2(C6H4]WH, respectively. In contrast to the C-Si cleavage achieved by MeLi, Bu nLi, and PhLi, the ansa bridge of [Me2Si(Cp Me2)2]W(H)Cl is inert to ButLi and the product obtained is the fulvene ("tuck-in") complex [Me2Si(Cp Me2)(η6-C5MeH2CH2)] WH derived from dehydrohalogenation.

UR - https://www.scopus.com/pages/publications/49649105020

U2 - 10.1073/pnas.0803089105

DO - 10.1073/pnas.0803089105

M3 - Article

C2 - 18635687

AN - SCOPUS:49649105020

SN - 0027-8424

VL - 105

SP - 11060

EP - 11065

JO - Proceedings of the National Academy of Sciences of the United States of America

JF - Proceedings of the National Academy of Sciences of the United States of America

IS - 32

ER -

Silicon-Carbon bond cleavage reactions of Ansa tungstenocene compounds: The [Me₂Si] bridge as a site for metallocene functionalization

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