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.

Experimental evidence from liquid semiconductors

1977 ◽  
Vol 55 (11) ◽  
pp. 1961-1967 ◽  
Author(s):  
J. E. Enderby
Keyword(s):  
Electronic Structure ◽  
Alkali Metal ◽  
Experimental Evidence ◽  
Atomic Structure ◽  
Alkali Metals ◽  
The Other ◽  
Ionic Bonding ◽  
Liquid Semiconductors ◽  
Close Interaction ◽  
Semiconducting Alloys

Two broad types of liquid semiconducting alloys will be discussed, namely those involving alkali metals (e.g., the Li–Pb and the Cs–Au system) and those in which a chalcogen is involved (e.g., Cu–Te or Ni–Te). It will be argued that relatively simple ionic bonding schemes in alkali metal systems must be replaced by more complicated ones in chalcogen based alloys. The close interaction between atomic structure on one hand, and the electronic structure on the other will be emphasized.

scholarly journals THE REDUCTIVE DIMERIZATION OF N-BENZYLIDENE ANILINE

1966 ◽  
Vol 44 (21) ◽  
pp. 2497-2502 ◽  
Author(s):  
James G. Smith ◽  
C. Doreen Veach
Keyword(s):  
Alkali Metal ◽  
Lithium Metal ◽  
Reaction Products ◽  
Polar Solvents ◽  
Reductive Dimerization ◽  
Nonpolar Solvents ◽  
Diastereomeric Mixture ◽  
Metal Adducts ◽  
Sodium And Potassium

The formation of alkali metal adducts of N-benzylidene aniline in several inert solvents is studied by protonolysis of the adducts and analysis of the reaction products, the diastereomeric N,N′,1,2-tetraphenylethylenediamines. With sodium and potassium metal in polar solvents, the product is predominantly the dd,ll diamine. With lithium metal or with solvents of low polarity, the product contains approximately equal quantities of the two diastereomers.It is demonstrated that the initially formed diastereomeric mixture generally contains appreciable amounts of the meso isomer. In polar solvents with sodium, isomerization to the stable dd,ll diastereomer occurs. However, with lithium or with sodium in nonpolar solvents, the isomerization does not occur. The reasons for the preponderance of the dd,ll-disodio compound in the equilibrating systems are discussed.

On the atomic volume relations in certain isomorphous series. III.

1929 ◽  
Vol 22 (124) ◽  
pp. 70-76
Author(s):  
A. F. Hallimond
Keyword(s):  
Alkali Metal ◽  
Internal Pressure ◽  
Alkali Metals ◽  
Alkali Halides ◽  
Atomic Volume ◽  
Free Alkali ◽  
Large Measure ◽  
Accurate Knowledge ◽  
Sodium And Potassium ◽  
Large Contraction

Accurate knowledge of the compressibility of solids was first due in a large measure to the investigations of T. W. Richards, who showed that the pressure-volume curves for sodium and potassium approximate in form to rectangular hyperbolae, that the compressibilities of the free alkali metals are nearly proportional to the atomic volumes, and that the atoms can be treated as filling the available space. Richards then endeavoured to calculate the relative volumes of the combined elements in the alkali halides, assuming that the large contraction which takes place on forming the compound was due to an internal pressure which affected equally the alkali metal and the halogen.

THE ELECTRONIC SPECTRA OF SOME ANIONIC POLYMERIZATION SYSTEMS

1964 ◽  
Vol 42 (6) ◽  
pp. 1255-1260 ◽  
Author(s):  
S. Bywater ◽  
A. F. Johnson ◽  
D. J. Worsfold
Keyword(s):  
Alkali Metal ◽  
Absorption Spectra ◽  
Anionic Polymerization ◽  
Electronic Spectra ◽  
Alkali Metals ◽  
Ultraviolet Absorption ◽  
Tetrahydrofuran Solution ◽  
Sodium And Potassium

The ultraviolet absorption spectra of living anionic polymerizing systems have been measured with sytrene, butadiene, and isoprene as the monomers; with lithium, sodium, and potassium as the alkali metals; and with tetrahydrofuran, cyclohexane, and benzene as the solvents. For any monomer the similarity of the spectra obtained with the various metals and solvents leads to the conclusion that the alkali metal – carbon band has the same structure under the various conditions. From other evidence the bond is considered to be ionic in all cases. The diene monomer anions in tetrahydrofuran solution were found to undergo a series of isomerizations, some of them comparable in speed to the consumption of monomer.

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.

Diffusion of Alkali Metals in SiC

2014 ◽  
Vol 778-780 ◽  
pp. 297-300 ◽  
Author(s):  
Margareta K. Linnarsson ◽  
Anders Hallén
Keyword(s):  
Mass Spectrometry ◽  
Alkali Metal ◽  
Ion Implantation ◽  
Alkali Metals ◽  
Secondary Ion Mass Spectrometry ◽  
Temperature Range ◽  
Metal Diffusion ◽  
Induced Defects ◽  
Secondary Ion ◽  
Sodium And Potassium

Diffusion of lithium, sodium and potassium in SiC has been studied by secondary ion mass spectrometry. The alkali metal diffusion sources have been introduced by ion implantation. Subsequent anneals have been carried out in vacuum or in Ar atmosphere in the temperature range 700 °C - 1500 °C for 5 min to 16 h. The bombardment-induced defects in the vicinity of the ion implanted profile are readily decorated by the implanted . In the bulk, the diffusing alkali metals are most likely trapped and detrapped at boron and/or other defects during diffusion. The diffusivity of the studied alkali metals decreases as the mass increases, Li+<Na+<K+, but the sodium mobility in SiC is substantial already at 1100 °C.

Lithium - Heavier alkali metal exchange in organolithium compounds induced by alkoxides of heavier alkali metals and reactions occurring in this system

1988 ◽  
Vol 53 (1) ◽  
pp. 76-96 ◽  
Author(s):  
Lubomír Lochmann ◽  
Jiří Trekoval
Keyword(s):  
Alkali Metal ◽  
Exchange Reaction ◽  
Alkali Metals ◽  
Metal Exchange ◽  
Metal Alkoxides ◽  
Individual State ◽  
Organolithium Compounds ◽  
Reactive Compound ◽  
The Individual ◽  
Derivatives Of

Organolithium compounds of various types undergo an exchange reaction lithium-heavier alkali metal when treated with heavier alkali metal alkoxides. In the presence of a third reactive compound the exchange reaction gives rise to a compound of the third component substituted with the heavier alkali metal. Using this exchange reaction, organic derivatives of heavier alkali metals in the individual state can be easily prepared. The mechanism of such reactions is discussed, and the formation of lithium alkoxide is assumed to contribute significantly to the driving force of the reaction. Organic compounds of heavier alkali metals possess a considerably higher reactivity than organolithium compounds, and are therefore used as reactive intermediates in preparative chemistry, or as polymerization initiators in macromolecular chemistry. This review provides information about the scope and possibilities of this exchange reaction, which has been increasingly widely used in the recent years.

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

1974 ◽  
Vol 52 (18) ◽  
pp. 3259-3268 ◽  
Author(s):  
G. A. Salmon ◽  
W. A. Seddon ◽  
J. W. Fletcher
Keyword(s):  
Alkali Metal ◽  
Alkali Metals ◽  
Dissociation Constants ◽  
Alkali Metal Cation ◽  
Ion Pairs ◽  
Alkali Metal Cations ◽  
Solvated Electrons ◽  
Sodium Potassium ◽  
Sodium And Potassium ◽  
Metal Anions

Pulse radiolysis of solutions of alkali metal cations in tetrahydrofuran (THF) demonstrates the formation of solvated electrons es−, alkali metal cation-ion pairs (M+, es−), and alkali metal anions M−. This paper describes the spectra, extinction coefficients, and radiolytic yields of es−, lithium, sodium, potassium, and cesium species in THF. The reaction kinetics are complex but largely involve reactions A and B[Formula: see text]with the concomitant disappearance of all three species by reaction with radiolytically produced radicals. Rate constants and ion-pair dissociation constants for es− and the sodium and potassium species are presented and compared with data established from studies of blue solutions of alkali metals dissolved in THF.

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. I. The sodium and potassium adducts

1970 ◽  
Vol 48 (12) ◽  
pp. 1904-1914 ◽  
Author(s):  
E. J. MacPherson ◽  
James G. Smith
Keyword(s):  
Electron Transfer ◽  
Alkali Metal ◽  
Methyl Iodide ◽  
Chemical Reactions ◽  
Methyl Benzoate ◽  
Ethyl Chloroformate ◽  
Methylene Iodide ◽  
Benzylic Carbon ◽  
Metal Adducts ◽  
Sodium And Potassium

Contrary to previous reports, the reaction between benzophenone azine and sodium or potassium produces an adduct containing 2 g-atoms of alkali metal per mole of azine. The chemical reactions of this dianion have been examined and a 1,2-dianionic structure is most consistent with its chemical behavior.Treatment of the adduct with methyl iodide, 1,3-dibromopropane, or 1,4-dibromobutane results in alkylation on the benzylic carbon and adjacent nitrogen. However, regeneration of benzophenone azine occurred with methylene iodide, 1,2-dibromoethane, and benzyl chloride.With ethyl chloroformate, reaction occurred at the carbanionic center to form an intermediate unstable anion. This anion could be protonated or alkylated but if allowed to stand, decomposed to diphenyldiazomethane and the anion of ethyl diphenylacetate.Reaction of the benzophenone azine dianion with methyl benzoate is quite complicated and leads to substantial amounts of benzophenone azine being regenerated by electron transfer. That portion of the dianion which is not converted to azine reacts with methyl benzoate to produce the anion of α-benzamido- α,α-diphenylacetophenone.The possibility that an adduct of N-benzoyl benzophenone imine is an intermediate in this last reaction is examined and rejected.

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