Halide with alkali halides

The eutectic mixtures of the other aluminum halides with alkali halides also have low melting points (of about 100°C). The phase diagram of the A1C13-NaCl system is given in Figure 40 [390], The phase diagrams of A1C13 mixtures with other alkali metal chlorides have similar shapes. 

Uranium can be prepared by reducing uranium halides with alkali or alkaline earth metals or by reducing uranium oxides by calcium, aluminum, or carbon at high temperatures. The metal can also be produced by electrolysis of KUF5 or UF4, dissolved in a molten mixture of CaCl2 and NaCl. High-purity uranium can be prepared by the thermal decomposition of uranium halides on a hot filament. 

The reaction of BF with alkali halides yields the respective alkali fluoroborates (34) ... 

Dithiophosphato metal complexes are usually prepared by metathesis of metal halides with alkali metal or ammonium salts. A convenient method uses the redox reaction of his th iophosphory 1 )d is ulfanes (RO)2(S)PSSP(S)(OR)2, with metal species in low oxidation states resulting in the insertion of the metal into the sulfur-sulfur bond.24 Recently it was used for the synthesis of long alkyl chain, liquid platinum(II) dithiophosphates25 and for the synthesis of Ru (CO)2[S2P(OPr%]2 from Ru3(CO)i2 with (Pr 0)2(S)PSSP(S)(0Pr,)2.26... 

Metal dithiophosphinato complexes are usually prepared by metathesis of metal halides with alkali metal or ammonium dithiophoshinates, but can also be conveniently prepared by reactions of /i .v(thiophosphinyl)disul fanes, R2(S)PSSP(S)R2, with metal species.87 The electrochemical oxidation of metals in acetonitrile solution, in the presence of diphenylphosphine and sulfur affords M(S2PPh2)2 (M = Co, Zn, Cd),88 but this is not a preparative method. 

Two diacetylenes have been epitaxially polymerized as thin films in contact with alkali halide substrates. These films in contact with alkali halide substrates. These films consisted of highly oriented single crystals aligned along both <110> directions of the substrate. The structures of both poly(TCDU) and poly(DMDA) were modified by this technique and, in all cases, highly crystalline near-perfect films were achieved. 

T.M. Brown, R.H. Friend, I.S. Millard, D.J. Lacey, T. Butler, J.H. Burroughes, and F. Cacialli, Electronic line-up in light-emitting diodes with alkali-halide/metal cathodes, J. Appl. Phys., 93 6159-6172 (2003). 

Table II. Catalytic Activity of Sandwich Ligands 1 and 2 in Nucleophilic Substitutions on n-Octyl Methanesulfonate with Alkali Halides (MY) under Solid-Liquid Conditions in Toluene at 50°C...

This conclusion falls in line with the fact that the anion radical could neither be detected after collision of the parent halide with alkali metal atoms in the gas phase (Compton et ai, 1978) nor upon y-irradiation in apolar or weakly polar solid matrixes at 77 K by esr spectroscopy (Symons, 1981). However, these observations are not absolute proofs that the anion radicals do not exist they might exist and be too short lived to be detectable. On the other hand, the reaction medium and the driving force conditions are quite different from those in the electrochemical experiments, which rendered necessary an independent investigation of the problem in the latter. 

The synthesis of aliphatic nitro compounds from the reaction of alkyl halides with alkali metal nitrites was discovered by Kornblum and co-workers and is known as the modified Victor Meyer reaction or the Kornblum modification. The choice of solvent in these reactions is crucial when sodium nitrite is used as the nitrite soiuce. Both alkyl halide and nitrite anion must be in solution to react, and the higher the concentration of nitrite anion, the faster the reaction. For this reason, both DMF and DMSO are widely used as solvents, with both able to dissolve appreciable amounts of sodium nitrite. Although sodium nitrite is more soluble in DMSO than DMF the former can react with some halide substrates.Urea is occasionally added to DMF solutions of sodium nitrite to increase the solubility of this salt and hence increase reaction rates. Other alkali metal nitrites can be used in these reactions, like lithium nitrite,which is more soluble in DMF than sodium nitrite but is also less widely available. 

This activated zinc would be an aggregation of very fine zinc particles dispersed in the DMF solution. The size of these particles is smaller than that obtained in the previous process, which was performed in the absence of naphthalene12. This electrochemical method is comparable to the chemical Rieke procedure in which the activated zinc is prepared by reduction of zinc halide with alkali metal naphthalenide in THF13. 

Rieke reported in the early 1970s the preparation of highly reactive metal forms by the reduction of metal halides with alkali metals19. In the original work, anhydrous ZnBr2 in dry THF was refluxed for 4 h with potassium affording a finely divided slurry of an air-sensitive reactive metal, denoted as Zn (equation 5)43. 

With alkali halide-TBA-W or alkali halide-PD-W systems, the parameters Bne are negative for volumes and heat capacities (see Figures 1-5 and 10). This sign seems to be the one usually observed for the interaction of a hydrophobic with a hydrophilic solute (6). At intermediate cosolvent concentration, AYe°(W — W + TBA) and AYe°(W — W + PD) deviate in the direction we would expect for hydrophobic association the volume increases sharply, and the heat capacity decreases further. Inorganic electrolytes lower the critical micelle concentration of surfactants by salting out the monomers, thus favoring micellization (25) in a similar way, in the co-sphere of a hydrophilic ion, the hydrophobic bonding between the cosolvent molecules may be enhanced. 

Volatile protactinium pentaehloride has been prepared in a vacuum by reaction of the oxide with phosgene at 550° C or with carbon tetrachloride at 200°C. Reduction of this at 600°C with hydrogen leads to protactinium(IV) tetrachloride, Pad. which is isostructural with uranium(IV) tetrachloride, UCI4. The pentaehloride can be converted into the bromide or iodide by heating with the corresponding hydrogen halide or alkali halide... 

Organotin oxides, R2SnO or (RjSnLO, prepared by treatment of the organotin halides with alkali. 

Elimination-addition reactions of aryl halides with alkali-metal amides are discussed in Section 14-6C high-temperature copper-catalyzed amination, also effective, usually does not lead to rearrangement. 

In addition to the bimetallic complexes of rhenium and alkaline metals formed as byproducts in the exchange reactions of rhenium halids with alkali alkoxides (such as, for example, LiReO(OPr )5 xLiCl(THF)2 [519]) there has been recently prepared a number ofbimetallic complexes ofrhenium and molybdenum, rhenium and tungsten, and rhenium and niobium [904, 1451]. The latter are formed either due to the formation of a metal-metal bond, arising due to combination of a free electron pair on rhenium (V) and a vacant orbital of molybdenum (VI) atom or via insertion of molybdenum or tungsten atoms into the molecular structure characteristic of rhenium (V and VI) oxoalkox-ides. The formation of the compounds with variable composition becomes possible in the latter case. 

W.B. Miller, S.A. Safron, D.R. Herschbach, Exchange reactions of alkali atoms with alkali halides—A collision complex mechanism, Discuss. Faraday Soc. 44 (1967) 108. 

The reactions of alkaline earth atoms with alkali halide molecules are especially noteworthy because laser-induced fluorescence has been employed in these crossed-molecular beam experiments to measure the product internal state distributions as a function of scattering angle. For Ba + KC1 and Ca + NaCl, both the atomic and diatomic products were detected. 

The dynamics of the alkaline earth metal reactions with alkali halides appear to closely resemble the exchange reactions of alkali atoms with alkali halides [208, 216, 296] for which no direct energy disposal measurements have been reported. They proceed through a long-lived collision complex which is identified with a well in the reaction potential-energy surface. 

Metal alkyls will also react with alkali halides with the formation of a hydrocarbon and a metal salt ... 

For DRIFT studies, a wood wafer, paper sheet, or milled wood sample dispersed in KBr (or KC1) is placed in a cup at the focal point of the concave, ellipsoidal mirror so that the incident light is focused on the sample. The scattered light coming from the sample is collected from the concave mirror and directed by a suitable mirror system to the detector of the FTIR instrument. The pressure used for smoothing the sample has to be adjusted so that reproducible results can be obtained (Yeboah et al. 1984). The contribution of specular reflectance can be diminished by reducing the particle size and by increasing the sample dilution. For powder samples, as indicated above, the diluent is KBr or KCI. Good results are normally obtained with alkali halide powders that contain 1-2% of sample. In certain cases, the sample concentration may be increased up to 10%. 

Beryllium chloride is prepared by passing CCLt over BeO at 800°C. On a small scale the pure chloride and bromide are best prepared by direct interaction in a hot tube. The white crystalline chloride (mp 405°C) dissolves exothermically in water from HC1 solutions the salt [Be(H20)4]Cl2 can be obtained. Beryllium chloride is readily soluble in oxygenated solvents such as ethers. In melts with alkali halides, chloroberyllate ions [BeCl4]2 may be formed, but this ion does not exist in aqueous solution. 

Normally made by interaction of ions or halides with alkali polysulfides, they can be formed from sulfur, as in the reaction ... 

Alkoxide and aryloxide ligands are excellent ligands for the actinides. As a result, these ligands have been studied extensively in the coordination chemistry and reactivity of tri-, tetra-, penta-, and hexavalent actinides. The alkoxides and aryloxides can be synthesized by a variety of routes the two most popular routes include direct reaction of actinide halides with alkali metal salts of the alkoxide or aryloxide of interest and protonolysis of actinide amides by alcohols. 

One common present day preparation of dialkyl mono-and ditellurides involves the reaction of alkyl halides with alkali metal tellurides that have been prepared in situ. The reactions are commonly carried out in aqueous or nonaqueous solutions. Solutions of sodimn in liquid ammonia also provide a useful media for the reduction of tellurium. ... 

The halides have been the starting materials in the majority of syntheses, with alkali halide elimination ( 5.8.4.3.1) probably accounting for about half of all reported preparations. Chlorides and bromides are most commonly used and use of fluorides is rare. 

This silylamide route has attracted enormous attention as pure alkoxide complexes may be obtained directly [23]. The success of this reaction hinges upon the volatility of the amine byproduct that drives the reaction to completion [24]. Apotential concern is that the amide starting complexes are prepared by the reaction of lanthanide halides with alkali metal amides. High-purity, halide-free amides are thus critical to the success of this synthetic method. 

The metathesis reaction of anhydrous lanthanide halide with alkali metal alkoxo-functionalized NHC complex has recently proven to be another efficient and straightforward route to lanthanide NHC complexes (Equation 8.18) [69]. 

Wurtz-Fittig reactions are C-C coupling reactions of alkyl halides with alkali metals. This synthetic procedure is often applied for Si-Si coupling of silicon halides. See (a) A. Wurtz, Ann. Chim. Phys. 44, 275 (1855). (b) B. Tollens, R. 

The reduction of tertiary cyclopropyl halides with alkali metal naphthalenides leads to a similar situation. After treatment of a 78 22 and a 25 75 mixture, respectively, of r-1-bromo-l-methyl-c-2-methyl-r-2-phenylcyclopropane (110) and its isomer (111) with LiN in THE at 20°C, protonation with methanol led to identical 45 55 mixtures of r-l-phenyl-l,c-2-dimethyl- and r-1-phenyl-l,r-2-dimethylcyclopropanes (112 and 113). 

When treated with alkali halides, the corresponding p-aminophenyl-mereuric halides are formed, and with alkali hydroxides the hydroxide is produced. 

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