Ring Opening of Thiophene: Synthesis and Crystal Structure of Bis(diethyl ether)bis(μ4-{(3,4-η)-4-[1,1,3,3-tetramethyl-3-(2-thienyl)disilazan-1-yl-κN :κN]but-1-en-3-yne-1-thiolato(2−)-κS :κS :κS})tetralithium ([(C4H3S)SiMe2−N(Li)−SiMe2−C≡C−CH=CH−SLi⋅OEt2]2)

Veith, Michael; Koban, Astrid; Hüch, Volker

doi:10.1002/(sici)1522-2675(19980909)81:9<1640::aid-hlca1640>3.0.co;2-i

Cited by 6 publications

(3 citation statements)

References 10 publications

(16 reference statements)

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“…The presence of nonequivalent THF molecules suggests that the allylic side chain likely coordinates to only one of the two lithium atoms. Close contacts indicative of bonding interactions between lithium atoms and olefins have been observed in numerous crystal structures . The THF molecule that showed only a single peak for its α-CH 2 had nOe correlations to TBDMS and n BuLi resonances exclusively.…”

Section: Discussionmentioning

confidence: 78%

On the Mechanism of THF Catalyzed Vinylic Lithiation of Allylamine Derivatives: Structural Studies Using 2-D and Diffusion-Ordered NMR Spectroscopy

2005

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N-Lithio-N-(trialkylsilyl)allylamines can be deprotonated in the presence of ethereal solvents exclusively at the cis-vinylic position to yield 3,N-dilithio-N-(trialkylsilyl)allylamines under mild conditions. Low temperature (1)H and (7)Li NMR ((1)H NOESY, TOCSY, (1)H/(7)Li HSQC, and DO-NMR) studies on the solution structure of 3,N-dilithio-N-(tert-butyldimethylsilyl)allylamine identified three major aggregates in THF (monomer, dimer and tetramer), but the aggregate structures failed to explain the solvent dependence and regiochemical outcome of the reaction. Low temperature (1)H NMR (NOESY, TOCSY, DO-NMR) studies on the solution structure of N-lithio-N-(tert-butyldimethylsilyl)allylamine in the presence of nBuLi identified amide/nBuLi mixed aggregates in both the ethereal solvent THF (1:1 dimer) and the hydrocarbon solvent toluene (1:3 tetramer). Addition of 2 equiv of THF to toluene solutions induces the formation of the same THF solvated 1:1 dimer as observed in neat THF. NMR evidence suggests that in THF the mixed aggregate has close contact between the olefin and the beta-CH(2) of nBuLi, while in the absence of THF, the allyl chain appears to be pointed away from the nearest nBuLi residues.

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Section: Discussionmentioning

confidence: 78%

On the Mechanism of THF Catalyzed Vinylic Lithiation of Allylamine Derivatives: Structural Studies Using 2-D and Diffusion-Ordered NMR Spectroscopy

2005

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“…The NMR data for compound 1 in solution are in accordance with the solid state structure, indicating that the molecule is more symmetric in solution than in the solid state (identical Me 3 Si-groups in solution, two different types of lithium atoms). A ring opening of the furane system by butyllithium, as reported for a double metalated chelating amide containing thiophene groups, 18 could not be observed.…”

Section: X-ray Structure Determination Of N-lithium-n-trimethylsilylf...mentioning

confidence: 71%

Coordination chemistry of furfurylsilylamides

Sachdev

Wagner

Preis

et al. 2002

J. Chem. Soc., Dalton Trans.

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“…In the case of sodium there are three known alkynyl compounds with such π -interactions that have been structurally characterized . Furthermore, lithium alkynyl π -interactions have been observed in compounds of transition metals and main group elements . To the best of our knowledge there is no known aluminum alkynyl compound in which the alkynyl group interacts with an alkali metal ion.…”

Section: Introductionmentioning

confidence: 99%

Organoaluminates with Three Terminal Phenylethynyl Groups and Their Interactions with Alkali Metal Cations

et al. 2002

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The synthesis of [K + ‚THF(2,6-iPr 2 C 6 H 3 N-(SiMe 3 )Al(CtCPh) 3 ) -] 2 (1), [Na + ‚THF (2, 4) with the corresponding phenylethynyl alkali metal salt is reported. In compound 1 the potassium (2, sodium) interacts with the CtC bonds of four phenylethynyl groups. A further coordination site of the potassium (sodium) is occupied by a THF molecule. Thus, the cation therein acts as a bridging moiety to form the dimer. In compound 3 each of the lithium cations is 2-fold coordinated by phenylethynyl ligands and two dioxane molecules. One of the dioxane molecules in 3 functions as a bridge forming the dimer. The herein described compounds are the first structurally characterized species having three terminal phenylethynyl groups bound to the aluminum atom.

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Ring Opening of Thiophene: Synthesis and Crystal Structure of Bis(diethyl ether)bis(μ4-{(3,4-η)-4-[1,1,3,3-tetramethyl-3-(2-thienyl)disilazan-1-yl-κN :κN]but-1-en-3-yne-1-thiolato(2−)-κS :κS :κS})tetralithium ([(C4H3S)SiMe2−N(Li)−SiMe2−C≡C−CH=CH−SLi⋅OEt2]2)

Cited by 6 publications

References 10 publications

On the Mechanism of THF Catalyzed Vinylic Lithiation of Allylamine Derivatives: Structural Studies Using 2-D and Diffusion-Ordered NMR Spectroscopy

On the Mechanism of THF Catalyzed Vinylic Lithiation of Allylamine Derivatives: Structural Studies Using 2-D and Diffusion-Ordered NMR Spectroscopy

Coordination chemistry of furfurylsilylamides

Organoaluminates with Three Terminal Phenylethynyl Groups and Their Interactions with Alkali Metal Cations

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