761. The solubility of alkali metals in ethers

Down, J. L.; Lewis, J.; Moore, B.; Wilkinson, Geoffrey

doi:10.1039/jr9590003767

Cited by 83 publications

(40 citation statements)

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“…Furthermore the pulse radiolysis results (see earlier) show that the formation of the ion-pair in [2] is diffusion controlled whereas the flash photolysis interpretation indicates -the contrary (8,39). Further experiments are in progress in an attempt to rationalize these puzzling discrepancies.…”

Section: Comparisons With Flash Photolysismentioning

confidence: 96%

“…In THF it is well established that [2] produces the 900 nm band with a second order rate constant k, = 7.9 x 10'' M-' s-' (10,12) Because of spectral overlap it is not possible to measure the corresponding rate constants in DG, DME, or TG. However, changes in spectra such as depicted in Figs.…”

Section: Figmentioning

confidence: 99%

“…The nature of the blue solutions of alkali metals in ethers has aroused considerable interest since their original discovery in 1957 (1,2). Optical (3), electron spin resonance (esr) (4,5), conductivity (6), flash photolysis (7)(8)(9), and pulse radiolysis (10)(11)(12) techniques have now clearly established the contribution of solvated electrons, e,-, cation-electron aggregates (M', e,-), and alkali metal anions M-to the chemistry of such solutions.…”

Section: Introductionmentioning

confidence: 99%

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Solvated electrons and the effect of coordination on the optical spectra of alkali metal cation – electron pairs in ethers

Seddon¹,

Fletcher²,

Sopchyshyn³

et al. 1977

Can. J. Chem.

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. 55,3356 (1977). Pulse radiolysis of tetrahydrofuran (THF), dimethoxyethane (DME), diglyme (DG), and triglyme (TG), results in the formation of solvated electrons, e,-, with optical band maxima h, , . 2 1840 nm. In the presence of alkali metal salts transient optical bands are observed with h,,. at -900 and 2 1600 nm. The latter bands are assigned to the formation of 'monomeric' species of stoichiometry M considered to be 'tight' and 'loose' ion-pairs, respectively. The proportion of 'loose' ion-pairs increases with decreasing temperature and increasing coordination of the solvent in the order THF << DME < DG < TG. These results demonstrate a good correlation with established electron spin resonance data in alkali metal solutions and substantiate the coexistence of at least two 'monomeric' species in DME and the glymes. THF << DME < DG < TG. Ces rksultats dkmontrent une bonne corrklation avec les donnkes ktablies par resonance de spin Clectronique en solutions de mktaux alkalins et justifient la coexistence d'au moins deux esptces "monorntres" dans le DME et les glymes.[Traduit par le journal]

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Section: Comparisons With Flash Photolysismentioning

confidence: 96%

Section: Figmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Solvated electrons and the effect of coordination on the optical spectra of alkali metal cation – electron pairs in ethers

Seddon¹,

Fletcher²,

Sopchyshyn³

et al. 1977

Can. J. Chem.

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“…THF Sol~itioizs Cotztairzing K -and NaBlue solutions of alkali metals in ethers were first reported by Down et al (25,26). Since that tinie solutions of potassium in T H F and D M E have been studied by electrical conductance (27).…”

Section: Reaction Kinetics and Molar Extinctionmentioning

confidence: 99%

Pulse Radiolytic Formation of Solvated Electrons, Ion-pairs, and Alkali Metal Anions in Tetrahydrofuran

Salmon¹,

Seddon²,

Fletcher³

1974

Can. J. Chem.

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. Can. 9. Chem. 52.3259(1974). Pulse radiolysis of solutions of alkali metal cations in tetrahydrofuran (THFj demonstrates the formation of solvated electrons e,-, alkali metal cation -ion pairs (M', e,-), and alkali metal anions M -. This paper describes the spectra, extinction coefficients, and radiolytic yields of es-, iithium, sodium, potassium, and cesium species in TFIF. The reaction kinetics are colnplex but largely involve reactions A and B with the concomitant disappearance of all three species by reaction with radiolytically produced radicals. Rate constants and ion-pair dissociation constants for e,-and the sodium and potassium species are presented and compared with data established from studies of blue solutions of alkali metals dissolved in THF. e,-+ M + (M+, e,-)

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“…[28][29][30] Furthermore, in most cases, it is hard to remove the solvents due to the strong coordination between the solvents and the Na + ions. [9,28,[30][31][32][33][34][35] In this paper, we report an improved synthesis method for unsolvated NaB 3 H 8 , which involves an improved method to disperse Na and a refined procedure to produce fresh THF·BH 3 . The procedure avoids toxic reagents such as Hg and B 2 H 6 , employs simple setup, and thus facilitates large-scale production of NaB 3 H 8 .…”

Section: Introductionmentioning

confidence: 99%

An improved synthesis of unsolvated NaB 3 H 8 and its application in preparing Na 2 B 12 H 12

Chen

et al. 2016

International Journal of Hydrogen Energy

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Octahydrotriborates are potential hydrogen storage materials and chemical vapor deposition precursors to boride films. Their syntheses have been quite challenging, however. In this paper, an improved facile route for the preparation of unsolvated sodium octahydrotriborate (NaB3H8), which is an important precursor to other octahydrotriborates and derivatives, is reported. The key steps in the synthesis involve dispersing Na finely in inert media and preparing fresh tetrahydrofuran (THF)·BH3 at room temperature. High purity unsolvated NaB3H8 can be obtained in tens of grams or more in one batch, depending on the reactor size. Using NaB3H8 as the precursor, sodium dodecaborate (Na2B12H12) has been successfully synthesized. Both octahydrotriborates and dodecaborates have been observed as intermediates during the thermal dehydrogenation of borohydrides, and their facile syntheses would facilitate mechanistic studies on the hydrogen storage of borohydrides, among other potential applications. Disciplines Engineering | Physical Sciences and Mathematics Publication DetailsChen, W., Wu, G., He, T., Li, Z., Guo, Z., Liu, H., Huang, Z. & Chen, P. (2016). An improved synthesis of unsolvated NaB3H8 and its application in preparing Na2B12H12. AbstractOctahydrotriborates are potential hydrogen storage materials and chemical vapor deposition precursors to boride films. Their syntheses have been quite challenging, however. In this paper, an improved facile route for the preparation of unsolvated sodium octahydrotriborate (NaB 3 H 8 ), which is an important precursor to other octahydrotriborates and derivatives, is reported. The key steps in the synthesis involve dispersing Na finely in inert media and preparing fresh tetrahydrofuran (THF)·BH 3 at room temperature. High purity unsolvated NaB 3 H 8 can be obtained in tens of grams or more in one batch, depending on the reactor size. Using NaB 3 H 8 as the precursor, sodium dodecaborate (Na 2 B 12 H 12 ) has been successfully synthesized. Both octahydrotriborates and dodecaborates have been observed as intermediates during the thermal dehydrogenation of borohydrides, and their facile syntheses would facilitate mechanistic studies on the hydrogen storage of borohydrides, among other potential applications.

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761. The solubility of alkali metals in ethers

Cited by 83 publications

References 0 publications

Solvated electrons and the effect of coordination on the optical spectra of alkali metal cation – electron pairs in ethers

Solvated electrons and the effect of coordination on the optical spectra of alkali metal cation – electron pairs in ethers

Pulse Radiolytic Formation of Solvated Electrons, Ion-pairs, and Alkali Metal Anions in Tetrahydrofuran

An improved synthesis of unsolvated NaB 3 H 8 and its application in preparing Na 2 B 12 H 12

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