Dissociative in ethers

Energies of a-C—H Bonds Dissociation in Ethers and Enthalpies of Secondary Alkylperoxyl Radical Reactions with Ethers [2]... 

The magnesium aluminum halide tends to dissociate in ethereal solvents to form magnesium and aluminum halides ... 

As in metalation with n-buty Ilithium, ether and THF accelerate the reaction markedly over the rate observed with hydrocarbon solvents. Eastham el al.4c suggest that in a hydrocarbon solvent the reagent exists as a polymer and that this dissociates in ether or THF. 

The salt most commonly used in Li-S batteries is LiTFSI, which exhibits good chemical, thermal and electrochemical stability (no corrosion of the aluminum in the window of potential of the sulfur electrode, no formation of hydrofluoric acid - HF). Similarly, because of its high degree of dissociation in ethers, it enables us to obtain good ionic conductivity values, of around 5xlO S/cm at 20°C. Hence, it constitutes an alternative to LiPFe salt which is used in conventional lithium-ion batteries but is not very soluble in ether solvents. 

The presence of free ethyllithium in appreciable concentrations in ether solutions of LiAl(C2Hs)4 is excluded on the basis of the observed Li magnetic resonance spectrum (42). On the other hand, Wittig and coworkers conclude that LiMg(C6Hs)3 is appreciably dissociated in ether at room temperature 19). 

Phenyldiazonium chloride and other similar diazonium compounds are very soluble in water, are completely insoluble in ether and other organic solvents, and are completely dissociated in aqueous solution to organic cations and inorganic anions (e.g., chloride ions) a convenient formulation is therefore, for example, CjHjNj+CP. 

Tellurium Tetrabromide. Tellurium tetrabromide [10031-27-3] TeBr, forms yellow hygroscopic crystals which decompose above 280°C and melt at 363°C under bromine vapor. It boils at 414—427°C, dissociating into TeBr2 and bromine. It is soluble in ether and chloroform but not in CCl, and is readily hydroly2ed in water. 

In the case of 1,3-diphenylisoindole (29), Diels-Alder addition with maleic anhydride is readily reversible, and the position of equilibrium is found to be markedly dependent on the solvent. In ether, for example, the expected adduet (117) is formed in 72% yield, whereas in aeetonitrile solution the adduet is almost completely dissociated to its components. Similarly, the addition product (118) of maleic anhydride and l,3-diphenyl-2-methjdi.soindole is found to be completely dissociated on warming in methanol. The Diels-Alder products (119 and 120) formed by the addition of dimethyl acetylene-dicarboxylate and benzyne respectively to 1,3-diphcnylisoindole, show no tendency to revert to starting materials. An attempt to extrude carbethoxynitrene by thermal and photochemical methods from (121), prepared from the adduct (120) by treatment with butyl-lithium followed by ethyl chloroform ate, was unsuccessful. 

Polymerization of t-butyl methacrylate initiated by lithium compounds in toluene yields 100% isotactic polymers 64,65), and significantly, of a nearly uniform molecular-weight, while the isotactic polymethyl methacrylate formed under these conditions has a bimodal distribution. Significantly, the propagation of the lithium pairs of the t-Bu ester carbanion, is faster in toluene than in THF. In hydrocarbon solvents the monomers seem to interact strongly with the Li+ cations in the transition state of the addition, while the conventional direct monomer interaction with carbanions, that requires partial dissociation of ion-pair in the transition state of propagation, governs the addition in ethereal solvents. 

The aggregation of lithium polydienes is disrupted in ethereal solvents and their studies provide information about the conformation of the active centers. The stability of ethereal solutions of polydiene salts is greatly improved at low temperatures, especially in the presence of salts suppressing their dissociation 126). Under these conditions the cis-isomer is the most abundant in equilibrated THF solutions, although... 

Similar information is available for other bases. Lithium phenoxide (LiOPh) is a tetramer in THF. Lithium 3,5-dimethylphenoxide is a tetramer in ether, but addition of HMPA leads to dissociation to a... 

Calculation of O—H Bond Dissociation Energies in Ether Hydroperoxides from Kinetic Data (See Table 2.8 and Table 7.16)... 

On substitution of allyllithium with methyl groups, the structures are distorted tt complexes becoming more jj -like. The previously described allyllithiums are contact ion pairs (CIP) whose dissociation is too low to permit study of the free carbanion. However, this is not the case for a more delocalized system such as 1,3-diphenylallyl whose lithium salts can exist as solvent separated ion pairs (SSIP) in ethereal solutions for which the organic moiety could be treated essentially as a free carbanion55 Boche and coworkers studied the effect of substitution at C(2) in their 1,3-diphenylallyl lithiums on the rotational barriers... 

The dimer 12 can only be dissolved in ether solvents, when it undergoes dissociation, as corroborated by cryoscopic measurements and 23Na NMR spectra (24). In contrast, the Narduster salt 14 cannot be dissolved in any common organic solvents without decomposition... 

Hydrogen cyanide (Table 15.1) is a colorless, flammable liquid or gas that boils at 25.7°C and freezes at minus 13.2°C. The gas rarely occurs in nature, is lighter than air, and diffuses rapidly. It is usually prepared commercially from ammonia and methane at elevated temperatures with a platinum catalyst. It is miscible with water and alcohol, but is only slightly soluble in ether. In water, HCN is a weak acid with the ratio of HCN to CN about 100 at pH 7.2, 10 at pH 8.2, and 1 at pH 9.2. HCN can dissociate into H+ and CN. Cyanide ion, or free cyanide ion, refers to the anion CN derived from hydrocyanic acid in solution, in equilibrium with simple or complexed cyanide molecules. Cyanide ions resemble halide ions in several ways and are sometimes referred to as pseudohalide ions. For example, silver cyanide is almost insoluble in water, as are silver halides. Cyanide ions also form stable complexes with many metals. 

The authors proposed the following picture of the silylene anion-radical formation. Treatment of the starting material by the naphthalene anion-radical salt with lithium or sodium (the metals are denoted here as M) results in two-electron reduction of >Si=Si< bond with the formation of >SiM—MSi< intermediate. The existence of this intermediate was experimentally proven. The crown ether removes the alkali cation, leaving behind the >Si - Si< counterpart. This sharply increases electrostatic repulsion within the silicon-silicon bond and generates the driving force for its dissociation. In a control experiment, with the alkali cation inserted into the crown ether, >Si — Si< species does dissociate into two [>Si ] particles. 

Until fairly recently, little was known of the stmcmres and properties of the organozinc compounds occurring as intermediates in varions reactions. Interestingly, the complexforming ability of organozinc componnds had already been recognized very early. In 1858, Wanklyn reported the formation of the ionic sodium triethylzinc complex. One year later, Frankland observed that the formation of dimethylzinc from methyl iodide and zinc was accelerated by the addition of dimethyl ether or diethyl ether. It appeared that separation of the dimethylzinc from the ether was impossible, bnt it lasted nntil 1962 when it was established that dimethylzinc and dimethyl ether form a 1 1 complex in solntion, which is appreciably dissociated in the vaponr phase. ... 

In conclusion, it has been shown that use of cryptates for the anionic polymerization of heterocyclic monomers leatis to a tremendous increase of the rates of polymerization. There are two main causes to the higher reaction rates observed with cryptates. The first one is a suppression of the association between ion pairs in the non polar media, and the second one is the possibility of ion pairs dissociation into free ions in ethereal solvents like THP or THF. By this way, it has been possible to make detailed studies of the propagation reaction for propylene sulfide, ethylene oxide, and cycloslloxanes. 

Preparation of a Complex Ammonium Salt of Copper(II). Dissolve 0.5 g of finely triturated copper(II) sulphate pentahydrate in 12.5 ml of a 15% ammonia solution. If the solution is turbid, filter it. Slowly add 7.5 ml of ethanol to the filtrate and let it stand for a few hours in the cold. Filter off the formed crystals, wash them first with a mixture of ethanol and a concentrated ammonia solution (1 1), and then with ethanol and ether. Dry them at room temperature. Into what ions does the product dissociate in the solution Consider the structure of the complex ion from the viewpoint of the valence bond theory. 

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