Solution, organolithiums

In solution, organolithium compounds exist as aggregates, with the degree of aggregation depending on the structure of the organic group and the solvent. The nature of the species present in solution can be studied by low-temperature NMR. n-Butyllithium in THF, for example, is present as a tetramer-dimer mixture. The tetrameric species is dominant. 

CH3)2N]3P0. M.p. 4°C, b.p. 232"C, dielectric constant 30 at 25 C. Can be prepared from dimethylamine and phosphorus oxychloride. Used as an aprotic solvent, similar to liquid ammonia in solvent power but easier to handle. Solvent for organolithium compounds, Grignard reagents and the metals lithium, sodium and potassium (the latter metals give blue solutions). 

Many organolithium compounds may be prepared by the interaction of lithium with an alkyl chloride or bromide or with an aryl bromide in dry ethereal solution In a nitrogen atmosphere ... 

As pointed out in Note 1 a nitrogen atmosphere is preferred for the preparation of organolithium compounds. In the present example exclusion of oxygen is attained fairly satisfactorily by keeping the solution at the reflux point throughout an atmosphere of ether vapour is thus maintained. 

This complex should be used when the organolithium is in solution in a hydrocarbon solvent. For organolithium reagents prepared in ether (see Note 4), the same complex may be used or, more conveniently, copper iodide (Cull can be used. The Cul purchased from Prolabo or Merck 4 Company, Inc. may be used directly. Other commercial sources of Cul (Fluka, Aldrich Chemical Company, Inc., Alfa Products, Morton/Thiokol, Inc.) furnish a salt which affords better results when purified. 1 mol of Cul is stirred for 12 hr with 500 ml of anhydrous tetrahydrofuran, then filtered on a sintered glass funnel ( 3), washed twice with 50 ml of anhydrous tetrahydrofuran, once with 50 ml of anhydrous ether and finally dried under reduced pressure (0.1 imO for 4 hr. 

Good yields of phosphines have been obtained by the simultaneous addition of an organolithium compound and an alkyl chloride to a solution of a cyclopolyphosphane (6). 

Transmetalation with Zn on a chiral lithiated alkyl carbamate had been reported by Taylor via addition of a solution of ZnCl2 to an in situ generated chiral organolithium (Scheme 8.10) [15]. 

Oxirane was added to the organolithium (probably in ether solution) at a temperature perhaps —40°C. The mixture was then allowed to warm up, went out of control and distributed itself widely. Presumably too much ethylene oxide had accumulated because of sluggish reaction at the low temperature. 

During addition of an ethereal solution of deuterium oxide (containing some peroxide) to a suspension of the organolithium reagent in pentane, a violent explosion occurred. This may have been initiated by the peroxide present, but probably... 

This compound was found, on investigation of an explosion in a syringe during transfer, to have a decomposition energy equivalent to that of commercial explosives. Slow decomposition, even at room temperature, becomes explosive above 100°C. Shock sensitive. Stable as hydrocarbon solution below 25% concentration. Recommended that this and related compounds be handled only in such solution. See FLUORINATED ORGANOLITHIUM COMPOUND... 

As documented in detail for organolithium species, ligand and donor play a key role in determining the degree of aggregation. Methyllithium adopts a hexameric structure in hydrocarbon solvents.13,15 In the presence of monodentate, donors such as THF or diethyl ether tetramers are observed, while the increase in donor denticity to 2 (1,1-Dimethoxyethane (DME), N,N,N, N -Tetramethylethylenediamine (TMEDA)) affords monomeric structures. Further documenting the differences between solution and solid states, [CH3Li]4 adopts a tetrameric structure in the latter.15,15a-15c... 

The combination of equimolar amounts of tris(trimethylsilyl)methyllithium and zinc bromide in a THF/diethyl ether mixture, Scheme 27, furnished tris(trimethylsilyl)methylzinc bromide, as a lithium bromide/ether adduct.43 The compound, which may also be formulated as a lithium alkyldibromozincate, showed no ligand redistribution reactions. It is monomeric in solution and can be treated with 1 equiv. of an organolithium reagent to afford heteroleptic diorganozinc compounds. 

Organolithium reagents have also been employed for the synthesis of novel bis(alkynyl)mercury derivatives. These include Hg(C=CCF3)263 and 46-48,64 which have been synthesized along with the bis(alkynyl)aurate analogs. Bis(alkynyl)mercury species such as 49 can also be obtained by reaction of monosubstituted alkynes with K2[Hgl4] in basic aqueous solutions.6 ... 

Related to these catalysts are the systems based on lanthanide metal systems or rare earth metal complexes [46, 47]. The main problem with these catalyst systems is their instability. When the catalyst solution is prepared by reachng a metallocene with an organolithium compound in a polar solvent, the prepared catalyst soluhon is unstable and decomposes quickly, even under a nitrogen atmosphere. The activity of these catalysts can be high only if the catalyst is added to the polymer soluhon immediately after preparation. Attempts have been made to overcome the stability problem by using an additive in the system to improve the stability and the activity of the catalyst [33-35, 41, 57, 58, 61]. Re-... 

---