With Alkali Metals

Diphenyl ditellurium reacts with sodium in liquid ammonia or in hexamethylphosphoric triamide at 120° under an atmosphere of nitrogen to produce sodium henzenetellurolate. Potassium benzenetellurolate was prepared from diphenyl ditellurium and potassium in liquid ammonia . The liquid ammonia solutions of the tellurolates can be used for further reactions. If another solvent is desired, the ammonia can be evaporated and the residue dissolved in the solvent of choice. 

Sodium 2-thiophenetelluroIate was produced when the corresponding ditelluride and sodium were heated under nitrogen at 110°. 

Lithium benzenetellurolate and lithium ethanetellurolate ° were more conveniently obtained from the corresponding diorgano ditellurium compounds and lithium at room temperature with anhydrous diethyl ether or tetrahydrofuran as reaction medium. The reductions are complete when the orange-red color of the ditellurium derivatives has faded to pale yellow. 

Sodium Benzcnetellurolate This reaction must be carried out under nitrogen or argon in an apparatus suitable for work with liquid ammonia. A filtered suspension of 0.35 g (15 mmol) of sodium in 25 ml of liquid ammonia is added to a suspension of 3.1 g (7.5 mmol) of diphenyl ditellurium in 75 ml of liquid ammonia. The blue color of the sodium/ammonia solution changes rapidly to yellow. The reaction is complete when the solid ditellurium compound has disappeared. The reaction mixture is then filtered, the ammonia is evaporated, and the grey residue is washed with petroleum ether yield 3.1 g (95%). 

Lithium Benzenetellurolate In a 250 ml, three-necked flask fitted with a high speed stirrer and a nitrogen inlet tube is placed a solution of 4.1 g (0.01 mol) of diphenyl ditellurium in 100 ml of tetrahydrofuran and the flask is flushed with nitrogen. 0.14 g (0.02 mol) of freshly cut, small pieces of lithium are added through the third neck which is then stoppered. A positive nitrogen pressure is maintained and the mixture is stirred at 20 for 6 h. Any unreacted lithium is then removed the yellow solution of lithium benzenetellurolate must be kept under nitrogen to prevent oxidation to diphenyl ditellurium. 

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Graphite reacts with alkali metals, for example potassium, to form compounds which are non-stoichiometric but which all have limiting compositions (for example K C) in these, the alkaU metal atoms are intercalated between the layers of carbon atoms. In the preparation of fluorine by electrolysis of a molten fluoride with graphite electrodes the solid compound (CF) polycarbon fluoride is formed, with fluorine on each carbon atom, causing puckering of the rings. 

Such water, and also that containing salts of multipositive metals, (usually sulphates), is said to be hard since it does not readily produce a lather with soap. Experiments with alkali metal salts can be performed to verify that the hardness is due to the presence of the multipositive metal ions and not to any of the anions present. The hardness due to calcium and magnesium hydrogencarbonates is said to be temporary since it can be removed by boiling ... 

Bromine has a lower electron affinity and electrode potential than chlorine but is still a very reactive element. It combines violently with alkali metals and reacts spontaneously with phosphorus, arsenic and antimony. When heated it reacts with many other elements, including gold, but it does not attack platinum, and silver forms a protective film of silver bromide. Because of the strong oxidising properties, bromine, like fluorine and chlorine, tends to form compounds with the electropositive element in a high oxidation state. 

Within the periodic Hartree-Fock approach it is possible to incorporate many of the variants that we have discussed, such as LFHF or RHF. Density functional theory can also be used. I his makes it possible to compare the results obtained from these variants. Whilst density functional theory is more widely used for solid-state applications, there are certain types of problem that are currently more amenable to the Hartree-Fock method. Of particular ii. Icvance here are systems containing unpaired electrons, two recent examples being the clci tronic and magnetic properties of nickel oxide and alkaline earth oxides doped with alkali metal ions (Li in CaO) [Dovesi et al. 2000]. 

This isomerization, which must proceed through a 1,2,3-trienylanine, is not "contra-thermodynamic", since with a catalytic amount of potassium tert.-butoxide the same result is obtained. Enyne ethers, H2C=CH-CsC-0R, undergo a similar conversion into HCeC-CH=CH-OR upon interaction with alkali metal amides in liquid NH3, followed by hydrolysis . Enyne sulphides, H2C=CH-CsC-SR, and the hydrocarbons H2C=CH-CsC-R (R = or phenyl) give only tars or polymeric products under... 

The Birch reductions of C C double bonds with alkali metals in liquid ammonia or amines obey other rules than do the catalytic hydrogenations (D. Caine, 1976). In these reactions regio- and stereoselectivities are mainly determined by the stabilities of the intermediate carbanions. If one reduces, for example, the a, -unsaturated decalone below with lithium, a dianion is formed, whereof three different conformations (A), (B), and (C) are conceivable. Conformation (A) is the most stable, because repulsion disfavors the cis-decalin system (B) and in (C) the conjugation of the dianion is interrupted. Thus, protonation yields the trans-decalone system (G. Stork, 1964B). 

Single-bond cleavage with molecular hydrogen is termed hydrogenolysis. Palladium is the best catalyst for this purpose, platinum is not useful. Desulfurizations are most efficiently per-formed with Raney nickel (with or without hydrogen G.R. Pettit, 1962 A or with alkali metals in liquid ammonia or amines. The scheme below summarizes some classes of compounds most susceptible to hydrogenolysis. 

Organometalhcs. Halosilanes undergo substitution reactions with alkali metal organics, Grignard reagents, and alkylaluininums. These reactions lead to carbon—siUcon bond formation. 

Derivatives of Antimony Pentabromide and Pentaiodide. The existence of SbBr and Sbl is in doubt, although from time to time they are reported in the Hterature (35). The existence of a 1 1 adduct, SbBr 0(0244 )2, however, is generally accepted. In addition, the SbBr ion is known, and from x-ray studies has been found to have a slightly distorted octahedral stmcture (36). Indeed, there are quite a number of complex bromoantimony compounds with alkali metals and organic bases, some of wliich contain Sb(V). Thus the quinuclidinium salt (C24423N44)4Sb2Br2g is actually made up of... 

Base catalysis is most effective with alkali metals dispersed on solid supports or, in the homogeneous form, as aldoxides, amides, and so on. Small amounts of promoters form organoalkali comnpounds that really contribute the catalytic power. Basic ion exchange resins also are usebil. Base-catalyzed processes include isomerization and oligomerization of olefins, reactions of olefins with aromatics, and hydrogenation of polynuclear aromatics. 

Hot corrosion is a rapid form of attack that is generally associated with alkali metal contaminants, such as sodium and potassium, reacting with sulfur in the fuel to form molten sulfates. The presence of only a few parts per million (ppm) of such contaminants in the fuel, or equivalent in the air, is sufficient to cause this corrosion. Sodium can be introduced in a number of ways, such as salt water in liquid fuel, through the turbine air inlet at sites near salt water or other contaminated areas, or as contaminants in water/steam injections. Besides the alkali metals such as sodium and potassium, other chemical elements can influence or cause corrosion on bucketing. Notable in this connection are vanadium, primarily found in crude and residual oils. 

Specific gravity is the weight of the fuel in relation to water. This property is important in the design of centrifugal fuel washing systems. Sulfur content is important in connection with emission concerns and in connection with the alkali metals present in the ash. Sulfur reacting with alkali metals forms compounds that corrode by a process labeled sulfidation. 

The doping of Ceo with alkali metals creates carriers at the Fermi level in the tiu-derived band and decreases the electrical resistivity p of pristine solid Ceo by several orders of magnitude. As x in Ma C6o increases, the resistivity p(.-r) approaches a minimum at x = 3.0 0.05 [9, 112], corresponding to a half-filled flu-derived conduction band. Then, upon further increase in x from 3 to 6, p x) again increases, as is shown in Fig. 11 for various alkali metal dopants... 

Hydrides — True hydrides (i.e., those in which the hydrogen is in its anionic or most reduced form) are salt-like compounds in which the hydrogen is combined with alkali metals, either alone as simple hydrides or in association with other elements as complex hydrides. Hydrides react with water to release hydrogen. 

Chemical Reactivity - Reactivity with Water No reaction Reactivity with Common Materials May attack some forms of plastics Stability During Transport Stable Neutralizing Agents for Acids and Caustics Not pertinent,- Polymerization Hazardous polymerization unlikely to occur except when in contact with alkali metals or metallo-organic compounds Inhibitor of Polymerization 10 -20 ppm tert-butylcatechol. 

In coating fullerenes with alkali metals, the stability of the cluster seemed to be determined primarily by the electronic configuration. The units C qM and C7oMg, where M is any alkali metal, proved to be exceptionally stable cluster building blocks. Coating a fullerene with more than 7 alkali metal atoms led to an even-odd alternation in the mass spectra, inter-... 

A competing reaction in any Birch reduction is reaction of the alkali metal with the proton donor. The more acidic the proton donor, the more rapid IS the rate of this side reaction. Alcohols possess the optimum degree of acidity (pKa ca. 16-19) for use in Birch reductions and react sufficiently slowly with alkali metals in ammonia so that efficient reductions are possible with them. Eastham has studied the kinetics of reaction of ethanol with lithium and sodium in ammonia and found that the reaction is initially rapid, but it slows up markedly as the concentration of alkoxide ion in the mixture... 

Reduction with metal deuteride complexes (section Ill-A) is undoubtedly the most convenient way to convert carbonyl compounds into the corresponding deuterated alcohols. For stereochemical reasons, however, it is sometimes necessary to resort to reductions with alkali metals in O-deuterated alcohols, or in liquid deuterioammonia-O-deuterioalcohol mixtures. 

Ethynylation of the totally synthetic racemic 18-methyl-17-ketone (63) with acetylene and potassium t-butoxide in t-butanol-toluene or with alkali metal acetylide in liquid ammonia gives a low yield of rac-18-methyl-17a-ethynyl-3-methoxyestra-l,3,5(10)-trien-17/ -ol (64). 

Raman spectra have also been reported on ropes of SWCNTs doped with the alkali metals K and Rb and with the halogen Br2 [30]. It is found that the doping of CNTs with alkali metals and halogens yield Raman spectra that show spectral shifts of the modes near 1580 cm" associated with charge transfer. Upshifts in the mode frequencies are observed and are associated with the donation of electrons from the CNTs to the halogens in the case of acceptors, and downshifts are observed for electron charge transfer to the CNT from the alkali metal donors. These frequency shifts of the CNT Raman-active modes can in principle be u.sed to characterise the CNT-based intercalation compound for the amount of intercalate uptake that has occurred on the CNT wall. 

Tanuma, S., Synthesis and structure of quasi-one-dimensional carbon crystal carbolite and intercalation with alkali metals and halogens. In Supercarbon, Synthesis, Properties and Applications, ed. S. Yoshimura and R. P. H. Chang, Springer-Verlag, Heidelberg, 1998, pp. 120 127. 

In the reactions of 10.13a with alkali metal terr-butoxides cage expansion occurs to give the sixteen-atom cluster 10.15, in which two molecules of MO Bu (M = Na, K) are inserted into the dimeric structure. The cluster 10.13a also undergoes transmetallation reactions with coinage metals. For example, the reactions with silver(I) or copper(I) halides produces complexes in which three of the ions are replaced by Ag" or Cu" ions and a molecule of lithium halide is incorporated in the cluster. ... 

Figure 4.11 Molecular structures of typical crown-ether complexes with alkali metal cations (a) sodium-water-benzo-I5-crown-5 showing pentagonal-pyramidal coordination of Na by 6 oxygen atoms (b) 18-crown-6-potassium-ethyl acetoacetate enolate showing unsymmelrical coordination of K by 8 oxygen atoms and (c) the RbNCS ion pair coordinated by dibenzo-I8-crown-6 to give seven-fold coordination about Rb.

Electron addition to BiqHh can be achieved by direct reaction with alkali metals in ethers, benzene or liquid NH3 ... 

Reaction with alkali metals in liquid NH3 leads to reductive coupling to give colourless crystals of... 

With alkali metal hydroxides, both N2O and N2 are formed in addition to the nitrite ... 

Reacidification reprecipitates AS2S3 quantitatively. With alkali metal or ammonium polysulfides thioarsenates are formed which are virtually insoluble even in hot cone HCl ... 

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