Vibrational study of ionic association in aprotic solvents. 11. Formation and structure of mixed aggregates between lithium halides and lithium thiocyanate

Góralski, Paweł; Chabanel, Martial

doi:10.1021/ic00260a032

Cited by 26 publications

(23 citation statements)

References 2 publications

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“…The general strategy for characterizing enolates and related O-lithiated species using the method of continuous variation finds its origins in studies of Chabanel,15 Gagne,16 Günther,17 Reich,4i and others 18,19. An ensemble of homo- and heteroaggregated enolates (eq 1) is monitored as a function of the mole fractions of enolate subunits ( A and B ) using 6 Li NMR spectroscopy 20.…”

Section: Resultsmentioning

confidence: 99%

Solution Structures of Lithium Enolates, Phenolates, Carboxylates, and Alkoxides in the Presence of N,N,N′,N′-Tetramethylethylenediamine: A Prevalence of Cyclic Dimers

et al. 2008

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The method of continuous variation was used to characterize lithium enolates, phenolates, carboxylates, and alkoxides solvated by N,N,N',N'-tetramethylethylenediamine (TMEDA). The method relies on characterizing an ensemble of homo-and heteroaggregates using 6 Li NMR spectroscopy. A combination of aggregate counts and symmetries, nearly statistical distributions, and quantitative parametric fits revealed that cyclic dimers are the dominant form. Non-statistical distributions favoring heteroaggregated dimers were observed when hindered enolates and lithium carboxylates were mixed with unhindered enolates. Nonstatistical distributions favoring homoaggregates observed when hindered (tertiary) alkoxides were paired with other O-lithiated forms were traced to the formation of higher aggregates (hexamers) of the tertiary alkoxides. Highly hindered lithium phenolates appear to form TMEDA-solvated monomers.

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Section: Resultsmentioning

confidence: 99%

Solution Structures of Lithium Enolates, Phenolates, Carboxylates, and Alkoxides in the Presence of N,N,N′,N′-Tetramethylethylenediamine: A Prevalence of Cyclic Dimers

et al. 2008

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“…8,9 In short, an ensemble generated from constitutionally similar species of unknown aggregation number ( A n and B n , eq 1) is monitored with NMR spectroscopy as a function of mole fraction X A or X B . The number of heteroaggregates attests to the aggregation state.…”

Section: Resultsmentioning

confidence: 99%

Sodium Diisopropylamide: Aggregation, Solvation, and Stability

Algera

Collum

2017

J. Am. Chem. Soc.

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The solution structure, stabilities, physical properties, and reactivities of sodium diisopropylamide (NaDA) in a variety of coordinating solvents are described. NaDA is stable for months as a solid or as a 1.0 M solution in N,N-dimethylethylamine (DMEA) at −20 °C. A combination of NMR spectroscopic and computational studies show that NaDA is a disolvated symmetric dimer in DMEA, N,N-dimethyl-n-butylamine, and N-methylpyrrolidine. Tetrahydrofuran (THF) readily displaces DMEA, affording a tetrasolvated cyclic dimer at all THF concentrations. Dimethoxyethane (DME) and N,N,N′,N′-tetramethylethylenediamine (TMEDA) quantitatively displace DMEA, affording doubly chelated symmetric dimers. The trifunctional ligands N,N,N′,N″,N″-pentamethyldiethylenetriamine and diglyme bind the dimer as bidentate rather than tridentate ligands. Relative rates of solvent decompositions are reported, and rate studies for the decomposition of THF and DME are consistent with monomer-based mechanisms.

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“…[1] The relative arrangement of the bound ions depends on the spatial location of the binding sites, the choice of the ion-pair components, and the fashion in which the binding takes place (sequential/concurrent). [11][12][13][14] Calix [4]pyrroles and their derivatives are known to function as heteroditopic receptors for ion pairs. [9,10] Surprisingly, examples of the cooperative complexation of dimers of ion pairs and quartets of ions have not yet been described in the literature, despite the known existence of these species in solution.…”

Section: Virginia Valderrey Eduardo C Escudero-adµn and Pablo Ballmentioning

confidence: 99%

Highly Cooperative Binding of Ion‐Pair Dimers and Ion Quartets by a Bis(calix[4]pyrrole) Macrotricyclic Receptor

2013

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Vibrational study of ionic association in aprotic solvents. 11. Formation and structure of mixed aggregates between lithium halides and lithium thiocyanate

Cited by 26 publications

References 2 publications

Solution Structures of Lithium Enolates, Phenolates, Carboxylates, and Alkoxides in the Presence of N,N,N′,N′-Tetramethylethylenediamine: A Prevalence of Cyclic Dimers

Solution Structures of Lithium Enolates, Phenolates, Carboxylates, and Alkoxides in the Presence of N,N,N′,N′-Tetramethylethylenediamine: A Prevalence of Cyclic Dimers

Sodium Diisopropylamide: Aggregation, Solvation, and Stability

Highly Cooperative Binding of Ion‐Pair Dimers and Ion Quartets by a Bis(calix[4]pyrrole) Macrotricyclic Receptor

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