ChemInform Abstract: Dilithiodiethylgermane.

Bravo‐Zhivotovskii, Dmitry; PIGAREV, S. D.; Vyazankina, O. A.; Vyazankin, N. S.

doi:10.1002/chin.198824296

Cited by 4 publications

(5 citation statements)

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“…Preparations of 1a − c. Compound 1a was obtained in moderate yield (56%) by the treatment of 1,4-dichlorooctaisopropyltetrasilane with bis((trimethylsilyl)methyl)germylenedilithium, which was prepared by the reaction of bis((trimethylsilyl)methyl)bis(trimethylsilyl)germane, (Me 3 SiCH 2 ) 2 Ge(SiMe 3 ) 2 , with lithium in HMPA (see Experimental Section). The use of bis(trimethylsilyl)dialkylgermane as a starting material may provide a new convenient method for the preparation of dialkylgermylenedi(alkalimetal), because the latter compound had been prepared by the reaction of R 2 GeCl 2 with potassium in low yield (Bu 2 GeK 2 , 22%) or via many steps from R 2 GeHLi and Me 3 SiLi (Et 2 GeLi 2 , 73%) . Compounds 1b , c were synthesized by the reaction of the corresponding 1,4-dichlorooctaalkyltetrasilane with (diphenylgermylene)dipotassium9a in moderate to good yields (46 and 61%, respectively) 9b…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Structure, and Photolysis of Germatetrasilacyclopentanes

et al. 1998

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The five-membered-ring systems germatetrasilacyclopentanes [R2Si]4GeR‘2 (1) (1a, R = i-Pr, R‘ = Me3SiCH2; 1b, R = i-Pr, R‘ = Ph; 1c, R = t-BuCH2, R‘ = Ph) were synthesized and characterized. The structures of 1b,c have been determined by X-ray crystallography. The Si4Ge rings of 1b,c form an envelope and a distorted half-chair conformation, respectively. The photolysis of 1 using two kinds of light sources (low- and high-pressure mercury lamps) was carried out. The photochemical decomposition of 1a afforded two types of four-membered-ring products, cyclotetrasilane (Si4; main) and germatrisilacyclobutane (Si3Ge; minor), with extrusion of germylene (Ge:) and silylene (Si:), respectively. Compounds 1b,c gave, besides the four-membered-ring products as in 1a, two types of three-membered products, cyclotrisilanes (Si3) and disilagermiranes (Si2Ge), with extrusion of silagermene (SiGe) and disilene (SiSi), respectively. This is the first case in which the unusual decomposition of five-membered rings into three-membered rings and dimetallenes has been found.

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Section: Resultsmentioning

confidence: 99%

Synthesis, Structure, and Photolysis of Germatetrasilacyclopentanes

et al. 1998

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“…Vyazankin et al. generated Et 2 GeLi 2 (compound 3 b , Scheme 2) by the reaction of (Me 3 Si)Et 2 GeLi with Me 3 SiLi [12] . However, due to their thermal instability, these compounds were not isolable and were only identified by trapping reactions.…”

Section: Methodsmentioning

confidence: 99%

“…generated Et 2 GeLi 2 (compound 3 b , Scheme 2 ) by the reaction of (Me 3 Si)Et 2 GeLi with Me 3 SiLi. [12] However, due to their thermal instability, these compounds were not isolable and were only identified by trapping reactions. Sekiguchi and Lee used silylated precursor molecules to perform either a reductive cycloreversion or a direct reductive dehalogenation to synthesize isolable 1,1‐dilithiogermane derivatives (compound 4 , Scheme 1 ).…”

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Isolable Geminal Bisgermenolates: A New Synthon in Organometallic Chemistry

et al. 2021

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We have synthesized the first isolable geminal bisenolates L2K2Ge[(CO)R]2 (R=2,4,6‐trimethylphenyl (2 a,b), L=THF for (2 a) or [18]‐crown‐6 for (2 b)), a new synthon for the synthesis of organometallic reagents. The formation of these derivatives was confirmed by NMR spectroscopy and X‐ray crystallographic analysis. The UV/Vis spectra of these anions show three distinct bands, which were assigned by DFT calculations. The efficiency of 2 a,b to serve as new building block in macromolecular chemistry is demonstrated by the reactions with two different types of electrophiles (acid chlorides and alkyl halides). In all cases the salt metathesis reaction gave rise to novel Ge‐based photoinitiators in good yields.

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“…The formation of (diphenylgermyl)dilithium has been noted, without comment, in the reaction of lithium with diphenylgermane in HMPA using a method analogous to that described for Ph 2 GeK 2 8b. More recently, the preparation of Et 2 GeLi 2 by a very difficult route has been described 3a,b The reaction of 2 equiv of n -BuLi with 1a followed by alkylation with MeI gave the expected dimethyl derivative 4a almost quantitatively (eq 4).…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of New Lithiated Organogermanium Compounds

et al. 1996

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New (8-methoxy-1-naphthyl)arylgermanes 1a−c are synthesized. The crystal structure of 1b (aryl = mesityl), determined by X-ray diffraction, shows that an intramolecular interaction occurs between the oxygen and germanium atoms, the Ge- - -O distance being 2.75 Å. The corresponding (diarylgermyl)lithiums R2HGeLi are prepared in high yield by hydrogermolysis of tert-butyllithium in THF and are susprisingly stable. Their characterization by 1H, 13C, and 7Li NMR spectroscopy is reported. Dimetalation of the initial arylgermanes depends upon steric hindrance around the germanium atom and the nature of the organolithium compound RLi. The reaction of 1a or 1c with n-BuLi followed by MeI affords the expected dialkylation product, whereas 1b gives the unexpected iodide 5b due to steric hindrance around the germanium atom.

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ChemInform Abstract: Dilithiodiethylgermane.

Cited by 4 publications

References 0 publications

Synthesis, Structure, and Photolysis of Germatetrasilacyclopentanes

Synthesis, Structure, and Photolysis of Germatetrasilacyclopentanes

Isolable Geminal Bisgermenolates: A New Synthon in Organometallic Chemistry

Synthesis and Characterization of New Lithiated Organogermanium Compounds

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