Crystal structures of organometallic compounds of lithium and magnesium containing the bulky ligands C(SiMe3)2(SiMe2X) X=Me, Ph, NMe2, or C5H4N-2

Salih S. Al-Juaid; Anthony G. Avent; Colin Eaborn; Salima M. El-Hamruni; Simon A. Hawkes; Michael S. Hill; Martijn Hopman; Peter B. Hitchcock; J. David Smith

doi:10.1016/S0022-328X(01)01032-4

Crystal structures of organometallic compounds of lithium and magnesium containing the bulky ligands C(SiMe₃)₂(SiMe₂X) X=Me, Ph, NMe₂, or C₅H₄N-2

Salih S. Al-Juaid, Anthony G. Avent, Colin Eaborn, Salima M. El-Hamruni, Simon A. Hawkes, Michael S. Hill, Martijn Hopman, Peter B. Hitchcock, J. David Smith

University of Sussex

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

25 Citations (SciVal)

Abstract

The complex [Li(TMEDA){C(SiMe₃)₂SiMe₂NMe₂}] (1) (TMEDA=N,N,N′,N′-tetramethylethane-1,2,-diamine) was found to crystallise with an internally coordinated structure like that of [Li(THF)₂{C(SiMe₃)₂SiMe₂NMe ₂}] (THF=tetrahydrfuran). In contrast, the compound with Ph in place of NMe₂ crystallised as a dialkyllithate [Li(TMEDA)₂][Li{C(SiMe₃)₂(SiMe ₂Ph)}₂] (4). The reaction of 4 with MgBr₂ gave the doubly bromide-bridged lithium-magnesium complex [Li(TMEDA)(μ-Br)₂Mg{C(SiMe₃)₂(SiMe ₂Ph)}(THF)] (6), and that of [Li(THF){C(SiMe₃)₂(SiMe₂C₅H ₄N-2)}] gave the singly bridged compound [Li(THF)₃(μ-Br)MgBr{C(SiMe₃)₂(SiMe ₂C₅H₄N-2)] (8). The Grignard reagents [Mg{C(SiMe₃)₃}I(OEt₂)]₂ (10) and [Mg{C(SiMe₃)₂ (SiMe₂Ph)}I(OEt₂)]₂ (11) were obtained from the reactions between (Me₃Si)₃CI and (Me₂Ph)(Me₃Si)CI, respectively, with magnesium metal and shown to have halide-bridged structures. The unsymmetrical dialkylmagnesium [MgBu{C(SiMe₃)₂(SiMe₂NMe₂)}(THF)] (13), was prepared from a mixture of LiBu, 1 and [MgBr₂ (OEt₂)₂].

Original language	English
Pages (from-to)	76-86
Number of pages	11
Journal	Journal of Organometallic Chemistry
Volume	631
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(01)01032-4
Publication status	Published - 10 Aug 2001

Keywords

Bulky ligands
Lithium
Magnesium

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/S0022-328X(01)01032-4

Cite this

Al-Juaid, S. S., Avent, A. G., Eaborn, C., El-Hamruni, S. M., Hawkes, S. A., Hill, M. S., Hopman, M., Hitchcock, P. B., & Smith, J. D. (2001). Crystal structures of organometallic compounds of lithium and magnesium containing the bulky ligands C(SiMe₃)₂(SiMe₂X) X=Me, Ph, NMe₂, or C₅H₄N-2. Journal of Organometallic Chemistry, 631(1-2), 76-86. https://doi.org/10.1016/S0022-328X(01)01032-4

Al-Juaid, SS, Avent, AG, Eaborn, C, El-Hamruni, SM, Hawkes, SA, Hill, MS, Hopman, M, Hitchcock, PB & Smith, JD 2001, 'Crystal structures of organometallic compounds of lithium and magnesium containing the bulky ligands C(SiMe₃)₂(SiMe₂X) X=Me, Ph, NMe₂, or C₅H₄N-2', Journal of Organometallic Chemistry, vol. 631, no. 1-2, pp. 76-86. https://doi.org/10.1016/S0022-328X(01)01032-4

@article{c3c9ea87010543b4adc9393bc7e4abd9,

title = "Crystal structures of organometallic compounds of lithium and magnesium containing the bulky ligands C(SiMe3)2(SiMe2X) X=Me, Ph, NMe2, or C5H4N-2",

abstract = "The complex [Li(TMEDA){C(SiMe3)2SiMe2NMe2}] (1) (TMEDA=N,N,N′,N′-tetramethylethane-1,2,-diamine) was found to crystallise with an internally coordinated structure like that of [Li(THF)2{C(SiMe3)2SiMe2NMe 2}] (THF=tetrahydrfuran). In contrast, the compound with Ph in place of NMe2 crystallised as a dialkyllithate [Li(TMEDA)2][Li{C(SiMe3)2(SiMe 2Ph)}2] (4). The reaction of 4 with MgBr2 gave the doubly bromide-bridged lithium-magnesium complex [Li(TMEDA)(μ-Br)2Mg{C(SiMe3)2(SiMe 2Ph)}(THF)] (6), and that of [Li(THF){C(SiMe3)2(SiMe2C5H 4N-2)}] gave the singly bridged compound [Li(THF)3(μ-Br)MgBr{C(SiMe3)2(SiMe 2C5H4N-2)] (8). The Grignard reagents [Mg{C(SiMe3)3}I(OEt2)]2 (10) and [Mg{C(SiMe3)2 (SiMe2Ph)}I(OEt2)]2 (11) were obtained from the reactions between (Me3Si)3CI and (Me2Ph)(Me3Si)CI, respectively, with magnesium metal and shown to have halide-bridged structures. The unsymmetrical dialkylmagnesium [MgBu{C(SiMe3)2(SiMe2NMe2)}(THF)] (13), was prepared from a mixture of LiBu, 1 and [MgBr2 (OEt2)2].",

keywords = "Bulky ligands, Lithium, Magnesium",

author = "Al-Juaid, {Salih S.} and Avent, {Anthony G.} and Colin Eaborn and El-Hamruni, {Salima M.} and Hawkes, {Simon A.} and Hill, {Michael S.} and Martijn Hopman and Hitchcock, {Peter B.} and Smith, {J. David}",

year = "2001",

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doi = "10.1016/S0022-328X(01)01032-4",

language = "English",

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issn = "0022-328X",

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T1 - Crystal structures of organometallic compounds of lithium and magnesium containing the bulky ligands C(SiMe3)2(SiMe2X) X=Me, Ph, NMe2, or C5H4N-2

AU - Al-Juaid, Salih S.

AU - Avent, Anthony G.

AU - Eaborn, Colin

AU - El-Hamruni, Salima M.

AU - Hawkes, Simon A.

AU - Hill, Michael S.

AU - Hopman, Martijn

AU - Hitchcock, Peter B.

AU - Smith, J. David

PY - 2001/8/10

Y1 - 2001/8/10

N2 - The complex [Li(TMEDA){C(SiMe3)2SiMe2NMe2}] (1) (TMEDA=N,N,N′,N′-tetramethylethane-1,2,-diamine) was found to crystallise with an internally coordinated structure like that of [Li(THF)2{C(SiMe3)2SiMe2NMe 2}] (THF=tetrahydrfuran). In contrast, the compound with Ph in place of NMe2 crystallised as a dialkyllithate [Li(TMEDA)2][Li{C(SiMe3)2(SiMe 2Ph)}2] (4). The reaction of 4 with MgBr2 gave the doubly bromide-bridged lithium-magnesium complex [Li(TMEDA)(μ-Br)2Mg{C(SiMe3)2(SiMe 2Ph)}(THF)] (6), and that of [Li(THF){C(SiMe3)2(SiMe2C5H 4N-2)}] gave the singly bridged compound [Li(THF)3(μ-Br)MgBr{C(SiMe3)2(SiMe 2C5H4N-2)] (8). The Grignard reagents [Mg{C(SiMe3)3}I(OEt2)]2 (10) and [Mg{C(SiMe3)2 (SiMe2Ph)}I(OEt2)]2 (11) were obtained from the reactions between (Me3Si)3CI and (Me2Ph)(Me3Si)CI, respectively, with magnesium metal and shown to have halide-bridged structures. The unsymmetrical dialkylmagnesium [MgBu{C(SiMe3)2(SiMe2NMe2)}(THF)] (13), was prepared from a mixture of LiBu, 1 and [MgBr2 (OEt2)2].

AB - The complex [Li(TMEDA){C(SiMe3)2SiMe2NMe2}] (1) (TMEDA=N,N,N′,N′-tetramethylethane-1,2,-diamine) was found to crystallise with an internally coordinated structure like that of [Li(THF)2{C(SiMe3)2SiMe2NMe 2}] (THF=tetrahydrfuran). In contrast, the compound with Ph in place of NMe2 crystallised as a dialkyllithate [Li(TMEDA)2][Li{C(SiMe3)2(SiMe 2Ph)}2] (4). The reaction of 4 with MgBr2 gave the doubly bromide-bridged lithium-magnesium complex [Li(TMEDA)(μ-Br)2Mg{C(SiMe3)2(SiMe 2Ph)}(THF)] (6), and that of [Li(THF){C(SiMe3)2(SiMe2C5H 4N-2)}] gave the singly bridged compound [Li(THF)3(μ-Br)MgBr{C(SiMe3)2(SiMe 2C5H4N-2)] (8). The Grignard reagents [Mg{C(SiMe3)3}I(OEt2)]2 (10) and [Mg{C(SiMe3)2 (SiMe2Ph)}I(OEt2)]2 (11) were obtained from the reactions between (Me3Si)3CI and (Me2Ph)(Me3Si)CI, respectively, with magnesium metal and shown to have halide-bridged structures. The unsymmetrical dialkylmagnesium [MgBu{C(SiMe3)2(SiMe2NMe2)}(THF)] (13), was prepared from a mixture of LiBu, 1 and [MgBr2 (OEt2)2].

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