Influence of a [Me2Si] ansa bridge on the barrier to rotation about the Zr-phenyl bond and on the generation and reactivity of benzyne intermediates: Comparison of the structures and reactivity of [Me2Si(C5Me4)2]Zr(Ph)X and Cp*2Zr(Ph)X (X = H, Cl, Ph)

Hyosun Lee; Brian M. Bridgewater; Gerard Parkin

doi:10.1039/b005117i

Influence of a [Me₂Si] ansa bridge on the barrier to rotation about the Zr-phenyl bond and on the generation and reactivity of benzyne intermediates: Comparison of the structures and reactivity of [Me₂Si(C₅Me₄)₂]Zr(Ph)X and Cp*₂Zr(Ph)X (X = H, Cl, Ph)

Hyosun Lee, Brian M. Bridgewater, Gerard Parkin

Columbia University

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

33 Scopus citations

Abstract

Comparison of the chemistry of [Me₂Si(C₅Me₄)₂]ZrPh₂ and Cp2ZrPh2 demonstrates that incorporation of a [Me₂Si] ansa bridge reduces the barrier for both (i) rotation about the Zr-Ph bond and (ii) elimination of benzene to generate a benzyne intermediate; furthermore, the [Me₂Si] ansa bridge promotes the reaction of two equivalents of MeCN with the benzyne intermediate {[Me₂Si(C₅Me₄)₂]Zr(η ²-C6H4)}, whereas insertion of only one equivalent is observed with [Cp*₂Zr(η²-C₆H₄)].

Original language	English
Pages (from-to)	4490-4493
Number of pages	4
Journal	Journal of the Chemical Society. Dalton Transactions
Issue number	24
DOIs	https://doi.org/10.1039/b005117i
State	Published - 2000

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Lee, H., Bridgewater, B. M., & Parkin, G. (2000). Influence of a [Me₂Si] ansa bridge on the barrier to rotation about the Zr-phenyl bond and on the generation and reactivity of benzyne intermediates: Comparison of the structures and reactivity of [Me₂Si(C₅Me₄)₂]Zr(Ph)X and Cp*₂Zr(Ph)X (X = H, Cl, Ph). Journal of the Chemical Society. Dalton Transactions, (24), 4490-4493. https://doi.org/10.1039/b005117i

Lee, Hyosun ; Bridgewater, Brian M. ; Parkin, Gerard. / Influence of a [Me₂Si] ansa bridge on the barrier to rotation about the Zr-phenyl bond and on the generation and reactivity of benzyne intermediates : Comparison of the structures and reactivity of [Me₂Si(C₅Me₄)₂]Zr(Ph)X and Cp*₂Zr(Ph)X (X = H, Cl, Ph). In: Journal of the Chemical Society. Dalton Transactions. 2000 ; No. 24. pp. 4490-4493.

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title = "Influence of a [Me2Si] ansa bridge on the barrier to rotation about the Zr-phenyl bond and on the generation and reactivity of benzyne intermediates: Comparison of the structures and reactivity of [Me2Si(C5Me4)2]Zr(Ph)X and Cp*2Zr(Ph)X (X = H, Cl, Ph)",

abstract = "Comparison of the chemistry of [Me2Si(C5Me4)2]ZrPh2 and Cp2ZrPh2 demonstrates that incorporation of a [Me2Si] ansa bridge reduces the barrier for both (i) rotation about the Zr-Ph bond and (ii) elimination of benzene to generate a benzyne intermediate; furthermore, the [Me2Si] ansa bridge promotes the reaction of two equivalents of MeCN with the benzyne intermediate {[Me2Si(C5Me4)2]Zr(η 2-C6H4)}, whereas insertion of only one equivalent is observed with [Cp*2Zr(η2-C6H4)].",

author = "Hyosun Lee and Bridgewater, {Brian M.} and Gerard Parkin",

year = "2000",

doi = "10.1039/b005117i",

language = "English",

pages = "4490--4493",

journal = "Journal of the Chemical Society. Dalton Transactions",

issn = "1470-479X",

publisher = "Royal Society of Chemistry",

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Lee, H, Bridgewater, BM & Parkin, G 2000, 'Influence of a [Me₂Si] ansa bridge on the barrier to rotation about the Zr-phenyl bond and on the generation and reactivity of benzyne intermediates: Comparison of the structures and reactivity of [Me₂Si(C₅Me₄)₂]Zr(Ph)X and Cp*₂Zr(Ph)X (X = H, Cl, Ph)', Journal of the Chemical Society. Dalton Transactions, no. 24, pp. 4490-4493. https://doi.org/10.1039/b005117i

Influence of a [Me₂Si] ansa bridge on the barrier to rotation about the Zr-phenyl bond and on the generation and reactivity of benzyne intermediates: Comparison of the structures and reactivity of [Me₂Si(C₅Me₄)₂]Zr(Ph)X and Cp*₂Zr(Ph)X (X = H, Cl, Ph). / Lee, Hyosun; Bridgewater, Brian M.; Parkin, Gerard.
In: Journal of the Chemical Society. Dalton Transactions, No. 24, 2000, p. 4490-4493.

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

TY - JOUR

T1 - Influence of a [Me2Si] ansa bridge on the barrier to rotation about the Zr-phenyl bond and on the generation and reactivity of benzyne intermediates

T2 - Comparison of the structures and reactivity of [Me2Si(C5Me4)2]Zr(Ph)X and Cp*2Zr(Ph)X (X = H, Cl, Ph)

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PY - 2000

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N2 - Comparison of the chemistry of [Me2Si(C5Me4)2]ZrPh2 and Cp2ZrPh2 demonstrates that incorporation of a [Me2Si] ansa bridge reduces the barrier for both (i) rotation about the Zr-Ph bond and (ii) elimination of benzene to generate a benzyne intermediate; furthermore, the [Me2Si] ansa bridge promotes the reaction of two equivalents of MeCN with the benzyne intermediate {[Me2Si(C5Me4)2]Zr(η 2-C6H4)}, whereas insertion of only one equivalent is observed with [Cp*2Zr(η2-C6H4)].

AB - Comparison of the chemistry of [Me2Si(C5Me4)2]ZrPh2 and Cp2ZrPh2 demonstrates that incorporation of a [Me2Si] ansa bridge reduces the barrier for both (i) rotation about the Zr-Ph bond and (ii) elimination of benzene to generate a benzyne intermediate; furthermore, the [Me2Si] ansa bridge promotes the reaction of two equivalents of MeCN with the benzyne intermediate {[Me2Si(C5Me4)2]Zr(η 2-C6H4)}, whereas insertion of only one equivalent is observed with [Cp*2Zr(η2-C6H4)].

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