Tris(trimethylsilyl)silyllithium · 3 THF: a stable crystalline silyllithium reagent

Gutekunst, G.; Brook, A. G.

doi:10.1016/s0022-328x(00)86805-9

Cited by 196 publications

(75 citation statements)

References 7 publications

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“…[LiSi(SiMe 3 ) 3 ·3THF] (1), was synthesized by a published procedure, [7] and was purified by recrystallization from npentane at Ϫ20°C to give colorless crystals. Lagow et al in 1990.…”

Section: Resultsmentioning

confidence: 99%

“…[5] Tris(trimethylsilyl)silyllithium (1), whose synthesis was first reported by Gilman and Smith in 1967 [6] and then modified by Brook in 1982, [7] has been well studied from the viewpoint of its molecular structure, [8] NMR spectroscopic behavior, [9] and its application to the synthesis of the first stable silene species, [10] polysilane dendrimers, [11] and transition metal complexes. [12] Interestingly, thermolysis of 1 leads to the formation of bis(trimethylsilyl)dilithiosilane, which was trapped by [D 1 ]-ethanol and iodomethane to give the corresponding dideuteriosilane and dimethylsilane, respectively.…”

Section: Introductionmentioning

confidence: 99%

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Tris(trimethylsilyl)‐Substituted Heavy Group 14‐Element‐Centered Anions: Unsolvated Trimeric Germyllithium and Solvated Dimeric Silyl‐ and Stannyllithiums

Nanjo

Mochida

2004

Eur J Inorg Chem

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Tris(trimethylsilyl)‐substituted group 14‐element‐centered anion monomers [LiE(SiMe3)3·3THF] (E = Si, Ge, and Sn) can be distilled under reduced pressure to give dimeric silyllithium 4 and stannyllithium 6, and trimeric germyllithium 5 without pyrolysis products such as dilithiometallanes. The molecular structures of 4, 5, and 6 were unequivocally determined by X‐ray diffraction. Dimer 4 has a symmetrical bent four‐membered‐ring structure consisting of two anionic silicon atoms and two cationic lithium atoms with coordinated THF molecules. Dimer 6 has an unsymmetrical distorted four‐membered‐ring structure consisting of two anionic tin atoms, a bridged unsolvated lithium atom, and a bridged lithium atom solvated by a THF molecule. Interestingly, 6 aggregates to form dimers of dimers by an intermolecular CH3···Li interaction. Trimeric germyllithium 5 forms an equilateral triangular lithium cluster without solvation. Compound 5 has a crystallographic threefold axis with three anionic germanium atoms and three cationic lithium atoms lying in the same plane. The lithium atoms in 5 are stabilized by an intramolecular CH3···Li interaction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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“…[LiSi(SiMe 3 ) 3 ·3THF] (1), was synthesized by a published procedure, [7] and was purified by recrystallization from npentane at Ϫ20°C to give colorless crystals. Lagow et al in 1990.…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Tris(trimethylsilyl)‐Substituted Heavy Group 14‐Element‐Centered Anions: Unsolvated Trimeric Germyllithium and Solvated Dimeric Silyl‐ and Stannyllithiums

Nanjo

Mochida

2004

Eur J Inorg Chem

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“…For example, reaction of LiMe with 7 and 10, respectively, generates after 2-3 days the highly air-and moisture-sensitive branched lithium silanides Li-18 [70,71] and Li-19 [72] ( Figure 4). Similarly, branched polysilane 21 [73] can be converted into Li-22 [74] in good yields ( Figure 5).…”

Section: Cores Spacers and Wingsmentioning

confidence: 99%

Polysilane Dendrimers

Krempner

2012

Polymers

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Abstract:The synthesis, structure and electronic properties of polysilane dendrimers, a relatively new class of highly branched and silicon-rich molecular architectures is reviewed. After a detailed discussion of main synthetic strategies to well-defined single-core and double-core polysilane dendrimers, important structural and conformational features determined by single crystal X-ray crystallography and 29 Si-NMR spectroscopy are presented. The last part highlights the most interesting photochemical properties of polysilane dendrimers such as UV absorption and emission behavior, which are compared with those of linear and branched polysilanes.

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“…Wie bei den Trimethylsilyl-Derivaten der Pnikogene [7,[2][3][4] und Chalkogene [5,8] wird auch hier mit Lithiummethyl die Spaltung nur einer E-Si-Bindung beobachtet (GI. (2)) [9,10]; Reaktionen mit dem aus solchen Ansätzen isolierten Etherat Lithium-tris(trimethylsilyl)silanid . 3 THF 2b führten in den zurückliegenden Jahren zu einer Reihe bemerkenswerter Folgeprodukte [11][12][13].…”

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Synthese und Struktur von Lithium‐tris(trimethylsilyl)silanid · 1,5 DME

Becker

Hartmann

Münch³

et al. 1985

Zeitschrift anorg allge chemie

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Synthesis and Structure of Lithium Tris (trimethylsilyl) silanide . 1,5 DME Abstract. Lithium tris(trimethylsilyl}silanide' 1,5 DME 2a synthesized from tetrakis(trimethylsilyl)silane 1 [6] and methyllithium in 1,2-dimethoxyethane 1 ), crystaIlizes in the monocIinic space group P2 1 /c with following dimensions of the unit cell determined at a temperature of measurement of -120 ± 2°C: a = 1072.9(3); b = 1408.3(4}; c = 1775.1(5} pm; ß = 107.74(2)°; 4 formula units (Z = 2). An X-ray structure determination (R w = 0.040) shows the compound to be built up from two [lithium tris(trimethylsilyl)silanide] moieties which are connected via a bridging DME moleeule. Two remaining sites of each four-coordinate lithium atom are occupied by a chelating DME ligand. The Li-Si distance of 263 pm is considerably longer than the sum oi covalent radii; further charactcristic mean bond lengths and angles are: Si-Si 234, Li-O 200, O-C 144, 0···0 (bite) 2G4pm; Si-Si--Si 104°, Li--Si-Si 107° to 126°; O-Li-O (inside the chelate ring) 83°. Unfortunately, di(tert-butyl)bis(trimethylsilyl)silane 17 prepared from di(tert-bntyl)dichlorsilane 15, chlorotrimethylsilane and lithium, does not react with alkyllithinm compounds to give the analogons silanide.

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Tris(trimethylsilyl)silyllithium · 3 THF: a stable crystalline silyllithium reagent

Cited by 196 publications

References 7 publications

Tris(trimethylsilyl)‐Substituted Heavy Group 14‐Element‐Centered Anions: Unsolvated Trimeric Germyllithium and Solvated Dimeric Silyl‐ and Stannyllithiums

Tris(trimethylsilyl)‐Substituted Heavy Group 14‐Element‐Centered Anions: Unsolvated Trimeric Germyllithium and Solvated Dimeric Silyl‐ and Stannyllithiums

Polysilane Dendrimers

Synthese und Struktur von Lithium‐tris(trimethylsilyl)silanid · 1,5 DME

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