Lithium compounds metalation

Uses. The largest use of lithium metal is in the production of organometaUic alkyl and aryl lithium compounds by reactions of lithium dispersions with the corresponding organohaHdes. Lithium metal is also used in organic syntheses for preparations of alkoxides and organosilanes, as weU as for reductions. Other uses for the metal include fabricated lithium battery components and manufacture of lithium alloys. It is also used for production of lithium hydride and lithium nitride. 

An emerging electrochemical appHcation of lithium compounds is in molten carbonate fuel ceUs (qv) for high efficiency, low poUuting electrical power generation. The electrolyte for these fuel ceUs is a potassium carbonate—hthium carbonate eutectic contained within a lithium aluminate matrix. The cathode is a Hthiated metal oxide such as lithium nickel oxide. 

About 65% of the lithium is used as a ceU-bath additive in aluminum production and in ceramics and glass. Lithium batteries enjoy increasing popularity leading to steady growth in this market. Other uses are in lubricants and synthetic mbber (46). Since lithium is a light, strong metal, it finds apphcations in aerospace metals and alloys where a light metal is needed (see Lithiumand lithium compounds). 

Lithium. Several processes for lithium [7439-93-2], Li, metal production have been developed. The Downs cell with LiCl—KCl electrolyte produces lithium ia much the same manner as sodium is produced. Lithium metal or lithium—aluminum alloy can be produced from a mixture of fused chloride salts (108). Granular Li metal has been produced electrochemically from lithium salts ia organic solvents (109) (see LiTHlUM AND LITHIUM compounds). 

The rearrangement of an ether 1 when treated with a strong base, e.g. an organo-lithium compound RLi, to give an alcohol 3 via the intermediate a-metallated ether 2, is called the Wittig rearrangement. The product obtained is a secondary or tertiary alcohol. R R can be alkyl, aryl and vinyl. Especially suitable substrates are ethers where the intermediate carbanion can be stabilized by one of the substituents R R e.g. benzyl or allyl ethers. 

Vinylic copper reagents react with CICN to give vinyl cyanides, though BrCN and ICN give the vinylic halide instead." Vinylic cyanides have also been prepared by the reaction between vinylic lithium compounds and phenyl cyanate PhOCN." Alkyl cyanides (RCN) have been prepared, in varying yields, by treatment of sodium trialkylcyanoborates with NaCN and lead tetraacetate." Vinyl bromides reacted with KCN, in the presence of a nickel complex and zinc metal to give the vinyl nitrile. Vinyl triflates react with LiCN, in the presence of a palladium catalyst, to give the vinyl nitrile." ... 

This type of metallic exchange is used much less often than 12-32 and 12-33. It is an equilibrium reaction and is useful only if the equilibrium lies in the desired direction. Usually the goal is to prepare a lithium compound that is not prepared easily in other ways, for example, a vinylic or an allylic lithium, most commonly from an organotin substrate. Examples are the preparation of vinyllithium from phenyl-lithium and tetravinyltin and the formation of a-dialkylamino organolithium compounds from the corresponding organotin compounds ... 

Lithium-transition metal compounds are formed by reactions of, e.g., Ni CDT ... 

The corrosion resistance of lithium electrodes in contact with aprotic organic solvents is due to a particular protective film forming on the electrode surface when it first comes in contact witfi tfie solvent, preventing further interaction of the metal with the solvent. This film thus leads to a certain passivation of lithium, which, however, has the special feature of being efiective only while no current passes through the external circuit. The passive film does not prevent any of the current flow associated with the basic current-generating electrode reaction. The film contains insoluble lithium compounds (oxide, chloride) and products of solvent degradation. Its detailed chemical composition and physicochemical properties depend on the composition of the electrolyte solution and on the various impurity levels in this solution. 

Organocadmium compounds can be prepared from Grignard reagents or organo-lithium compounds by reaction with Cd(II) salts.180 They can also be prepared directly from alkyl, benzyl, and aryl halides by reaction with highly reactive cadmium metal generated by reduction of Cd(II) salts.181... 

These observations (confirmed by AES studies) indicate that after longer oxidation times the top surface is completely covered by lithium compounds, i.e. that the oxidation of lithium has become dominant. This implies a depletion of the element within the metal surface, i.e. the presence of a soft surface layer. 

In fact, crystalline graphites usually cannot be operated in PC electrolytes, unless effective film forming electrolyte additives are used (see above) as propane gas evolution [35], creation of solvated graphite intercalation compounds (sGICs) [36], and graphite exfoliation take place. Recently [37, 38], it was found that propylene evolution is observed at graphite, while absent at lithium active metallic anodes, e.g., Sn and SnSb. 

Two main structural types have been identified for allyl alkali metal species solvated ions in the form of CIPs where a delocalized anion with metal coordination is perpendicular to the ligand plane,130-134 or unsolvated allylic lithium compounds displaying localized ligand systems with NMR spectra closely resembling those of alkenes.135-138... 

Lithium compounds, not lithium metal, are used in the treatment of some types of mental disorders. The chemical properties of lithium metal are very different from lithium compounds containing the ion, Li+. Li metal is very reactive with water, forming the strong base, LiOH, and hydrogen gas and releasing much heat, none of which are good for the human body. 

The donor-stabilized lead(n) dialkyl 54 is prepared in 65% yield by the reaction of the lithium compound 53 with Pb[N(SiMe3)2]2- The orange-red crystals of 54 are stable in the solid state in solution, they slowly decompose to deposit metallic lead at room temperature (Equation (20)). 

The development of electrospray ionization (ESI) enabled multiply charged ions, solvated ions, and metal-coordinated species to be formed in the gas phase. Recently, Kass and coworkers showed that collision-induced dissociation (CID) of RC02Li containing ions (e.g. 1) leads to the loss of carbon dioxide and the attachment of Li to R (Scheme 1) . This is an exceptionally stable alkyl lithium compound that could be synthesized, in the gas phase, under relatively mild conditions. 

---