Ambient Temperature Alkali Metal Transfer in Hydrocarbons - A New Route to Intercalation Compounds and Alloys

1982 ◽  
Vol 20 ◽  
Author(s):  
J.O. Besenhard ◽  
I. Kain ◽  
H.-F. Klein ◽  
H. MöHwald ◽  
H. Witty
Keyword(s):  
Alkali Metal ◽  
Ambient Temperature ◽  
Alkali Metals ◽  
Reducing Power ◽  
Metal Transfer ◽  
Intercalation Compounds ◽  
Transfer Reactions ◽  
Polar Solvents

ABSTRACTDissolved cobalt(0) complexes of the type [L3L'Co] (L = phosphanes, e.g. PMe3, L' = olefins, e.g. C2H4) are reversibly reduced by alkali metals A (A = Li, K, Rb, Cs)n[L3L'Co] + A ⇋ A[L3L'Co]and hence can be used as A-carriers. These carrier complexes A[L3L'Co]n are even soluble in apolar solvents like pentane.Action of [L3L'Co] plus A in pentane solution on graphite yields binary intercalation compounds ACn. By contrast, conventional ambient temperature A-transfer reagents (e.g. solutions of A in naphthalene-ether or in NH3) require strongly polar solvents and yield ternary intercalation compounds A(solv)yCn.The “reducing power” of the alkali cobaltates is close to that of free A: alkali-rich phases like 1st stage KC8 or LiC6 or highly doped polyacetylenes (e.g. K(CH)5) are readily prepared. If intercalation of solvated species is unlikely, the A-transfer reactions may also be performed in polar solvents like ethers.

scholarly journals Preparation of Alkali Metal-graphite Intercalation Compounds in the Solutions of Alkali Metals Dissolved in Dimethoxymethane or Diethoxyethane

TANSO ◽  
1998 ◽  
Vol 1998 (185) ◽  
pp. 262-265 ◽  
Author(s):  
Yasuo Mizutani ◽  
Takeshi Abe ◽  
Kazuhiro Ikeda ◽  
Minoru Inaba ◽  
Zempachi Ogumi ◽  
...  
Keyword(s):  
Alkali Metal ◽  
Alkali Metals ◽  
Intercalation Compounds ◽  
Graphite Intercalation Compounds ◽  
Graphite Intercalation

Electron transfer reactions from alkali metal surfaces to (±) and (S)-(−)-1,3-dimethoxy-1,1-diphenylbutane. Studies on 1,3-elimination

1984 ◽  
Vol 62 (11) ◽  
pp. 2464-2470 ◽  
Author(s):  
Harry M. Walborsky ◽  
Martha Pass Murari
Keyword(s):  
Electron Transfer ◽  
Alkali Metal ◽  
Charge Radius ◽  
Alkali Metals ◽  
Transfer Reactions ◽  
Lithium Metal ◽  
Sodium Metal ◽  
Pure Product ◽  
Optically Pure ◽  
Sodium And Potassium

The 1,3-elimination of methoxide by carbanions generated from the reaction of (±)-1,3-dimethoxy-1,1-diphenylbutane with the alkali metals, lithium, sodium, and potassium, in various solvents was studied to determine the significance of cation–methoxyl coordination due to decreasing charge/radius ratio of the cations and also the cation complexing ability of the solvent. The stereochemistry of cyclization in the reaction of (S)-(−)-1,3-dimethoxy-1,1-diphenylbutane with lithium metal in tetrahydrofuran and with sodium metal in methylcyclohexane to yield 1-methyl-2,2-diphenylcyclopropane was determined. The reaction proceeded by an intramolecular SN2-type displacement to yield optically pure product of inverted configuration.

Alkali metal adducts of benzophenone azine. II. The lithium adduct

1970 ◽  
Vol 48 (12) ◽  
pp. 1915-1918 ◽  
Author(s):  
E. J. MacPherson ◽  
James G. Smith
Keyword(s):  
Alkali Metal ◽  
Alkali Metals ◽  
Reducing Power ◽  
The Other ◽  
Organolithium Compounds ◽  
Metal Adducts ◽  
Sodium And Potassium

The behavior of benzophenone azine towards lithium has been studied. Unlike sodium and potassium, lithium effected extensive reduction and cleavage of benzophenone azine; the reaction product being benzhydryl amine. By limiting the amount of lithium to 2 g-atoms per mole of azine, the reaction product was shown to be N-lithiobenzophenone imine on the basis of its chemical behavior.Two reasons are advanced to explain the behavior of lithium in contrast to that of sodium or potassium. One explanation relies upon the greater reducing power of lithium compared with the other two alkali metals. The other relies upon the tendency of organolithium compounds to associate via formation of multi-center bonds.

Room Temperature Alkali Metal Reduction of Carbon Dioxide

2020 ◽  
Author(s):  
Lucas A. Freeman ◽  
Akachukwu D. Obi ◽  
Haleigh R. Machost ◽  
Andrew Molino ◽  
Asa W. Nichols ◽  
...  
Keyword(s):  
Alkali Metal ◽  
Alkali Metals ◽  
Room Temperature ◽  
Chemical Reduction ◽  
Bond Cleavage ◽  
Open Shell ◽  
Metal Reduction ◽  
One Pot ◽  
Earth Abundant ◽  
Electron Reduction

The reduction of the relatively inert carbon–oxygen bonds of CO<sub>2</sub> to access useful CO<sub>2</sub>-derived organic products is one of the most important fundamental challenges in synthetic chemistry. Facilitating this bond-cleavage using earth-abundant, non-toxic main group elements (MGEs) is especially arduous because of the difficulty in achieving strong inner-sphere interactions between CO<sub>2</sub> and the MGE. Herein we report the first successful chemical reduction of CO<sub>2</sub> at room temperature by alkali metals, promoted by a cyclic(alkyl)(amino) carbene (CAAC). One-electron reduction of CAAC-CO<sub>2</sub> adduct (<b>1</b>) with lithium, sodium or potassium metal yields stable monoanionic radicals clusters [M(CAAC–CO<sub>2</sub>)]<sub>n</sub>(M = Li, Na, K, <b> 2</b>-<b>4</b>) and two-electron alkali metal reduction affords open-shell, dianionic clusters of the general formula [M<sub>2</sub>(CAAC–CO<sub>2</sub>)]<sub>n </sub>(<b>5</b>-<b>8</b>). It is notable that these crystalline clusters of reduced CO<sub>2</sub> may also be isolated via the “one-pot” reaction of free CO<sub>2</sub> with free CAAC followed by the addition of alkali metals – a reductive process which does not occur in the absence of carbene. Each of the products <b>2</b>-<b>8</b> were investigated using a combination of experimental and theoretical methods.<br>

scholarly journals Spotlight on Alkali Metals: The Structural Chemistry of Alkali Metal Thallides

Crystals ◽  
2020 ◽  
Vol 10 (11) ◽  
pp. 1013
Author(s):  
Stefanie Gärtner
Keyword(s):  
Crystal Structure ◽  
Alkali Metal ◽  
Crystal Structures ◽  
Alkali Metals ◽  
Valence Electron ◽  
Oxidation States ◽  
Valence Electron Concentration ◽  
Base Metals ◽  
Charge Balancing

Alkali metal thallides go back to the investigative works of Eduard Zintl about base metals in negative oxidation states. In 1932, he described the crystal structure of NaTl as the first representative for this class of compounds. Since then, a bunch of versatile crystal structures has been reported for thallium as electronegative element in intermetallic solid state compounds. For combinations of thallium with alkali metals as electropositive counterparts, a broad range of different unique structure types has been observed. Interestingly, various thallium substructures at the same or very similar valence electron concentration (VEC) are obtained. This in return emphasizes that the role of the alkali metals on structure formation goes far beyond ancillary filling atoms, which are present only due to charge balancing reasons. In this review, the alkali metals are in focus and the local surroundings of the latter are discussed in terms of their crystallographic sites in the corresponding crystal structures.

New graphite intercalation compounds with heavy alkali metal superoxides

1996 ◽  
Vol 57 (6-8) ◽  
pp. 821-825 ◽  
Author(s):  
V.Z. Mordkovich ◽  
M. Baxendale ◽  
Y. Ohki ◽  
S. Yoshimura ◽  
T. Yamashita ◽  
...  
Keyword(s):  
Alkali Metal ◽  
Intercalation Compounds ◽  
Graphite Intercalation Compounds ◽  
Graphite Intercalation

Electronic Properties of Alkali-Metal-Hydrogen-Graphite Intercalation Compounds*

1992 ◽  
Vol 1 (1) ◽  
pp. 609-616
Author(s):  
Toshiaki Enoki ◽  
Kazuhiko Shindo ◽  
Noriaki Sakamoto ◽  
Keisuke Nakazawa ◽  
Kazuya Suzuki ◽  
...  
Keyword(s):  
Alkali Metal ◽  
Electronic Properties ◽  
Intercalation Compounds ◽  
Graphite Intercalation Compounds ◽  
Graphite Intercalation
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