Molecules mimicking atoms: monomers and dimers of alkali metal solvated electron precursors

2018 ◽  
Vol 20 (37) ◽  
pp. 24186-24191 ◽  
Author(s):  
Isuru R. Ariyarathna ◽  
Filip Pawłowski ◽  
Joseph Vincent Ortiz ◽  
Evangelos Miliordos
Keyword(s):  
Alkali Metal ◽  
Molecular Hydrogen ◽  
Solvated Electron ◽  
Neutral Species ◽  
Sodium Complexes

Tetra-amino lithium and sodium complexes M(NH3)0,−4 (M = Li, Na) have one or two electrons that occupy diffuse hydrogenic type orbitals distributed chiefly outside the M(NH3)4+ core. Two such neutral species can bind to form a dimer which can be seen as the analogue of molecular hydrogen.

Coordination of molecular hydrogen to alkali metal pentalenide complexes

2021 ◽  
pp. 139267
Author(s):  
Sharity Morales-Meza ◽  
María E. Sánchez-Castro ◽  
Marisol Ibarra-Rodríguez ◽  
Mario Sánchez
Keyword(s):  
Alkali Metal ◽  
Molecular Hydrogen

Pulse Radiolysis of Alkali Metal Solutions in Ethylamine

1973 ◽  
Vol 51 (17) ◽  
pp. 2975-2986 ◽  
Author(s):  
J. W. Fletcher ◽  
W. A. Seddon ◽  
F. C. Sopchyshyn
Keyword(s):  
Alkali Metal ◽  
Pulse Radiolysis ◽  
Electron Pair ◽  
Equilibrium Constants ◽  
Distinct Species ◽  
Complexing Agents ◽  
Crown Compounds ◽  
Solvated Electron ◽  
Sodium Potassium ◽  
Extinction Coefficients

Pulse radiolysis of solutions of alkali metal ethylamides in ethylamine shows the formation of three distinct species; the solvated electron es−, the alkali metal anion M−, and a species considered to be the cation–electron pair with stoichiometry M. The three species coexist in equilibrium in accord with the equations[Formula: see text]Studies of these solutions as a function of temperature, alkali metal concentration, and added complexing agents ("crown" compounds) show that es− and M have distinct absorption spectra with the former having a maximum ≥ 1800 nm. The latter exhibit maxima at 1400 nm for Na and K, ~1400 nm for Cs, and 1600–1700 nm for Li. The corresponding M− species were observed in sodium, potassium, and cesium solutions with absorption maxima at 680, 890, and 1100 nm, respectively.Rate and equilibrium constants for the formation of M and M− vary markedly with the nature of the alkali metal. Estimates for these constants along with the extinction coefficients for the various species are summarized and compared with data obtained in alkali metal solutions.

Pulse Radiolysis of Liquid Deuterated Ammonia

1973 ◽  
Vol 51 (22) ◽  
pp. 3653-3661 ◽  
Author(s):  
William Arthur Seddon ◽  
John Wallace Fletcher ◽  
John Jevcak ◽  
Fred Charles Sopchyshyn
Keyword(s):  
Alkali Metal ◽  
Time Scale ◽  
Pulse Radiolysis ◽  
Equilibrium Mixture ◽  
Solvated Electron ◽  
Metal Amides ◽  
Initial Yield ◽  
Metal Electron

Pulse radiolysis of solutions of alkali metal amides in deuterated ammonia at −15 °C produces an initial absorption with a maximum at 1500 nm due to the solvated electron, eam−. This decays on a microsecond time scale giving a residual long lived absorption with a slightly broader spectrum and a maximum displaced to 1640 nm. We suggest the residual absorption is an equilibrium mixture of eam− and a metal–electron species. The initial decay of eam− is suppressed by scavenging ND2 and/or ND− radicals with dissolved D2 (1 atm) or NaBH4. Evidence is also obtained for the reaction ND− + D2 → eam−. It is estimated that k(eam− + ND2) and k(BH4− + ND2) = 2.5 × 1010 and 7 × 107 M−l s−1, respectively. Measurements of the initial yield in NH3 and ND3 give [Formula: see text]and 3.6 ± 0.4 molecules/100 eV, respectively.

Primary mechanisms in the radiolysis of amines: pulse and γ-radiolysis of neutral and acidic ethylamine, n-propylamine and ethylenediamine

1979 ◽  
Vol 57 (15) ◽  
pp. 2013-2021 ◽  
Author(s):  
J. A. Delaire ◽  
J. R. Bazouin
Keyword(s):  
Allyl Alcohol ◽  
Molecular Hydrogen ◽  
Pulse Radiolysis ◽  
Solvated Electron ◽  
Infrared Band ◽  
Solvated Electrons ◽  
Upper Limits ◽  
Transient Spectra ◽  
Alkyl Ammonium

The transient spectra in pure ethylamine (EA), n-propylamine (nPA), and ethylenediamine (EDA) show, besides the visible and infrared band associated with the solvated electron, e−s, a small ultraviolet band attributed to oxidizing radicals. Upper limits for the recombination rate constants k of e−s with the acidic cation are 1.5 × 1012 L mol−1 and 3.5 × 1012 L mol−1s−1 in EA and nPA respectively, and k = 2 × 1010 L mol−1 s−1 in EDA. The yield of e−s at 3 ns (G(e−s)3ns = 1.5, 1.2, and 3.1 molecules/100 eV in EA, nPA, and EDA respectively) has been deduced by biphenyl scavenging. The yield of molecular hydrogen after γ-radiolysis G0(H2) = 5.7 and 3.6 in pure nPA and EDA respectively. The effect of solutes, such as biphenyl, alkyl-ammonium chloride, and allyl alcohol, on G(H2) is interpreted in terms of scavenging of e−s and/or H atoms. From the pulse-radiolysis determination of G(e−s), we deduce [Formula: see text] in nPA.Finally, the decay of solvated electrons seems to occur only via recombination with the cation in EA and nPA, but in EDA there is a competition between this reaction and reaction with oxidizing radicals.

Ethyl p-tert-butylcalix(4)arene ethanoate: The role of acetonitrile in the extraction of alkali-metal picrates and on the X-ray structures of the sodium complexes

2004 ◽  
Vol 6 (13) ◽  
pp. 3286 ◽  
Author(s):  
Angela F. Danil de Namor ◽  
Maria A. Pugliese ◽  
Alberto R. Casal ◽  
Walther B. Aparicio-Aragon ◽  
Oscar E. Piro ◽  
...  
Keyword(s):  
Alkali Metal ◽  
X Ray ◽  
Sodium Complexes
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