(Trimethylsilyl)methyllithium

(Trimethylsilyl)methyllithium
Identifiers
CAS Number	1822-00-0;
3D model (JSmol)	Interactive image;
ChemSpider	2723465;
ECHA InfoCard	100.157.622
EC Number	629-440-7;
PubChem CID	3482579;
CompTox Dashboard (EPA)	DTXSID90392901 ;
	InChI InChI=1S/C4H11Si.Li/c1-5(2,3)4;/h1H2,2-4H3;/q-1;+1 Key: KVWLUDFGXDFFON-UHFFFAOYSA-N;
	SMILES [Li+].C[Si](C)(C)[CH2-];
Properties
Chemical formula	C4H11LiSi
Molar mass	94.16 g·mol−1
Appearance	white or colorless solid
Density	0.937 g/cm3
Hazards
	GHS labelling:
Pictograms
Signal word	Danger
Hazard statements	H225, H314
Precautionary statements	P210, P233, P240, P241, P242, P243, P260, P264, P280, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P321, P363, P370+P378, P403+P235, P405, P501
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

(Trimethylsilyl)methyllithium is classified both as an organolithium compound and an organosilicon compound. It has the empirical formula LiCH₂Si(CH₃)₃, often abbreviated LiCH₂TMS. It crystallizes as the hexagonal prismatic hexamer [LiCH₂TMS]₆, akin to some polymorphs of methyllithium.^[2] Many adducts have been characterized including the diethyl ether complexed cubane [Li₄(μ₃-CH₂TMS)₄(Et₂O)₂]^[3] and [Li₂(μ-CH₂TMS)₂(TMEDA)₂].^[4]

Preparation

(Trimethylsilyl)methyllithium, which is commercially available as a THF solution, is usually prepared by treatment of (trimethylsilyl)methyl chloride with butyllithium:^[5]

(CH₃)₃SiCH₂Cl + BuLi → (CH₃)₃SiCH₂Li + BuCl

(Trimethylsilyl)methylmagnesium chloride is often functionally equivalent to (trimethylsilyl)methyllithium. It is prepared by the Grignard reaction of (trimethylsilyl)methyl chloride.^[6]^[7]

Use in methylenations

In one example of the Peterson olefination, (trimethylsilyl)methyllithium reacts with aldehydes and ketones to give the terminal alkene (R¹ = Me, R² & R³ = H):

Metal derivatives

Structure of the organoscandium complex with two (trimethylsilyl)methyl ligands, (C₅H₅)Sc(CH₂TMS)₂(THF).^[8] Color scheme: O (red), Sc (blue), Si (orange).

(Trimethylsilyl)methyllithium is widely used in organotransition metal chemistry to affix (trimethylsilyl)methyl ligands. Such complexes are usually produced by salt metathesis involving metal chlorides. These compounds are often highly soluble in nonpolar organic solvents, enjoying stability due to their steric bulk and resistance to beta-hydride elimination. In these regards, (trimethylsilyl)methyl is akin to neopentyl.

Bis(trimethylsilyl)methylmagnesium is used as an alternative to (trimethylsilyl)methyllithium.^[9]

Related compounds

bis(trimethylsilyl)methyllithium^[10]
tris(trimethylsilyl)methyllithium^[11]

References

^ "(Trimethylsilyl)methyllithium". pubchem.ncbi.nlm.nih.gov. Retrieved 12 January 2022.
^ Tecle', Berhan; Maqsudur Rahman, A.F.M.; Oliver, John P. (1986). "X-ray Crystal Structure of Trimethylsilylmethyllithium". Journal of Organometallic Chemistry. 317 (3): 267–275. doi:10.1016/0022-328X(86)80537-X.
^ Tatic, Tanja; Meindl, Kathrin; Henn, Julian; Pandey, Sushil Kumar; Stalke, Dietmar (2010). "The First Asymmetric Organolithium Tetramers with Simple Ether Donor Bases". Chemical Communications. 46 (25): 4562–4564. doi:10.1039/c002504f. PMID 20502820.
^ Tatic, Tanja; Ott, Holger; Stalke, Dietmar (2008). "Deaggregation of Trimethylsilylmethyllithium". European Journal of Inorganic Chemistry. 2008 (24): 3765–3768. Bibcode:2008EJIC.2008.3765T. doi:10.1002/ejic.200800610.
^ Age, David J.; Werth, Jacob (2019). "Trimethylsilylmethyllithium". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rt321. ISBN 978-0471936237.
^ Brennan, David J.; Graaskamp, James M.; Dunn, Beverly S.; Allcock, Harry R. (2007) [1989]. "Organosilicon Derivatives of Cyclic and High Polymeric Phosphazenes". Inorganic Syntheses. Vol. 25. pp. 60–68. doi:10.1002/9780470132562.ch15. ISBN 9780470132562.
^ Shioiri, Takayuki; Aoyama, Toyohik; Mori, Shigehiro (1990). "Trimethylsilyldiazomethane". Organic Syntheses. 68: 1. doi:10.15227/orgsyn.068.0001.
^ Li, Xiaofang; Nishiura, Masayoshi; Hu, Lihong; Mori, Kyouichi; Hou, Zhaomin (2009). "Alternating and Random Copolymerization of Isoprene and Ethylene Catalyzed by Cationic Half-Sandwich Scandium Alkyls". Journal of the American Chemical Society. 131 (38): 13870–13882. Bibcode:2009JAChS.13113870L. doi:10.1021/ja9056213. PMID 19728718.
^ Richard A. Andersen, Geoffrey Wilkinson (1979). "Bis[(Trimethylsilyl)Methyl] Magnesium". Inorganic Syntheses. Vol. 19. pp. 262–265. doi:10.1002/9780470132500.ch61. ISBN 9780470132500.
^ Jerry L. Atwood; Torgny Fjeldberg; Michael F. Lappert; N. Tuyet Luong-Thi; Riz Shakir; Andrew J. Thorne (1984). "Molecular structures of Bis(trimethylsilyl)methyl-lithium [(LiR), R = CH(SiMe₃)₂] in the Vapour (Gas-Phase Electron Diffraction: a Monomer, n= 1) and the Crystal (X-ray: a Polymer, n=∞)". Journal of the Chemical Society, Chemical Communications (17): 1163–1165. doi:10.1039/C39840001163.
^ Colin Eaborn; Peter B. Hitchcock; J. David Smith; Alice C. Sullivan (1983). "Crystal structure of the Tetrahydrofuran Adduct of Tris(trimethylsilyl)-Methyl-Lithium, [Li(thf)₄][Li{C(SiMe₃)₃}₂], an Ate Derivative of Lithium". Journal of the Chemical Society, Chemical Communications: 827–828. doi:10.1039/C39830000827.

[1] "(Trimethylsilyl)methyllithium". pubchem.ncbi.nlm.nih.gov. Retrieved 12 January 2022.

[2] Tecle', Berhan; Maqsudur Rahman, A.F.M.; Oliver, John P. (1986). "X-ray Crystal Structure of Trimethylsilylmethyllithium". Journal of Organometallic Chemistry. 317 (3): 267–275. doi:10.1016/0022-328X(86)80537-X.

[3] Tatic, Tanja; Meindl, Kathrin; Henn, Julian; Pandey, Sushil Kumar; Stalke, Dietmar (2010). "The First Asymmetric Organolithium Tetramers with Simple Ether Donor Bases". Chemical Communications. 46 (25): 4562–4564. doi:10.1039/c002504f. PMID 20502820.

[4] Tatic, Tanja; Ott, Holger; Stalke, Dietmar (2008). "Deaggregation of Trimethylsilylmethyllithium". European Journal of Inorganic Chemistry. 2008 (24): 3765–3768. Bibcode:2008EJIC.2008.3765T. doi:10.1002/ejic.200800610.

[5] Age, David J.; Werth, Jacob (2019). "Trimethylsilylmethyllithium". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rt321. ISBN 978-0471936237.

[6] Brennan, David J.; Graaskamp, James M.; Dunn, Beverly S.; Allcock, Harry R. (2007) [1989]. "Organosilicon Derivatives of Cyclic and High Polymeric Phosphazenes". Inorganic Syntheses. Vol. 25. pp. 60–68. doi:10.1002/9780470132562.ch15. ISBN 9780470132562.

[OS-7] Shioiri, Takayuki; Aoyama, Toyohik; Mori, Shigehiro (1990). "Trimethylsilyldiazomethane". Organic Syntheses. 68: 1. doi:10.15227/orgsyn.068.0001.

[8] Li, Xiaofang; Nishiura, Masayoshi; Hu, Lihong; Mori, Kyouichi; Hou, Zhaomin (2009). "Alternating and Random Copolymerization of Isoprene and Ethylene Catalyzed by Cationic Half-Sandwich Scandium Alkyls". Journal of the American Chemical Society. 131 (38): 13870–13882. Bibcode:2009JAChS.13113870L. doi:10.1021/ja9056213. PMID 19728718.

[RAA-9] Richard A. Andersen, Geoffrey Wilkinson (1979). "Bis[(Trimethylsilyl)Methyl] Magnesium". Inorganic Syntheses. Vol. 19. pp. 262–265. doi:10.1002/9780470132500.ch61. ISBN 9780470132500.

[10] Jerry L. Atwood; Torgny Fjeldberg; Michael F. Lappert; N. Tuyet Luong-Thi; Riz Shakir; Andrew J. Thorne (1984). "Molecular structures of Bis(trimethylsilyl)methyl-lithium [(LiR), R = CH(SiMe₃)₂] in the Vapour (Gas-Phase Electron Diffraction: a Monomer, n= 1) and the Crystal (X-ray: a Polymer, n=∞)". Journal of the Chemical Society, Chemical Communications (17): 1163–1165. doi:10.1039/C39840001163.

[11] Colin Eaborn; Peter B. Hitchcock; J. David Smith; Alice C. Sullivan (1983). "Crystal structure of the Tetrahydrofuran Adduct of Tris(trimethylsilyl)-Methyl-Lithium, [Li(thf)₄][Li{C(SiMe₃)₃}₂], an Ate Derivative of Lithium". Journal of the Chemical Society, Chemical Communications: 827–828. doi:10.1039/C39830000827.

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