Metal halides, replacement

Many reactions of fluorinated organics with metal halides result in the replacement of fluorine with halogen A general route to 1,1,1-trichloro- or tribromo-fluoroalkanes involves treating primary fluoroalkyl iodides with aluminum trichloride or aluminum tribromide [74], Benzylic [75, 76] or vinylic [72] fluorine can be exchanged for chlorine when treated with aluminum trichloride... 

Metal halides can in some cases, be used to replace other atoms or groups besides fluorine with halogen Polyfluoroacyl fluorides and chlorides can be converted to fluoroalkyl iodides by simply heating the reactant in the presence of an alkali metal iodide [[Pg.382]

Recently several pubhcations have examined replacing aqueous solvents with ionic liquids. Since simple and complex sugars are soluble in many imidazolium hahdes, water is not required as a co-solvent and degradation of HMF is minimal. Lansalot-Matras et al. reported on the dehydration of fmctose in imidazolium ionic liquids using acid catalyst (6). Moreau et al. reported that l-H-3-methylimidazolium chloride has sufficient acidity to operate without added acid (7). And we reported that a 0.5 wt% loading (6 mole% compared to substrate) of many metal halides in 1-ethyl-3-methylimidazohum chloride ([EMIM]C1) result in catalytically active materials particularly useful for dehydration reactions (8). 

Violent reactions can occur with many metal hahdes. For example, with zinc halides or iron halides, single replacement reactions take place. Such potassium-metal halide mixtures can react violently when subjected to mechanical shock. 

Mo and W hexacarbonyls, Mo(CO)6 and W(CO)6, alone do not induce polymerization of acetylenic compounds. However, UV irradiation toward these catalysts in the presence of halogenated compounds can form active species for polymerization of various substituted acetylenes. Carbon tetrachloride, CCI4, when used as the solvent for the polymerization, plays a very important role for the formation of active species, and thus cannot be replaced by toluene that is often used for metal chloride-based catalysts. Although these metal carbonyl-type catalysts are less active compared to the metal halide-based counterparts, they can provide high MW polymers. It is a great advantage that the metal carbonyl catalysts are very stable under air and thus handling is much easier. 

If we take a series of alkali metal halides, all with the rock salt structure, as we replace one metal ion with another, say sodium with potassium, we would expect the metal-halide internuclear distance to change by the same amount each time if the concept of an ion as a hard sphere with a particular radius holds true. Table 1.8 presents the results of this procedure for a range of alkali halides, and the change in internuclear distance on swapping one ion for another is highlighted. 

Nitrile complexes are obtained by dissolving a metal halide in the nitrile or by replacing CO from carbonyl complexes. A kinetic investigation of the reaction of acetonitrile on Group VI hexa-carbonyls22 showed that substitution by the first acetonitrile leads to increased replacement rates for the next two molecules. The second MeCN is built in cis to the first one, and replacement of the third CO gives /ac-Mo(CO)3(MeCN)3. Further substitution does not occur. The rate law comprises two terms and is of the form22 of equation (1). 

The products isolated from reactions of amides with transition metal halides usually contain coordinated halide (e.g. the formulations in Table 2). In some cases such as [Co(NMF)6][CoCLt], halide and amide are coordinated to different metal atoms, but when such compounds are dissolved in the neat ligand, halide can be replaced and at high dilution all the metal ions may be fully coordinated by the amide alone. The electronic spectrum resulting when this cobalt complex is dissolved in nitromethane has been interpreted as relating solely to the tetrahedral complex [CoC12(NMF)2]. 

Treatment of a primary alkyl halide or pseudohalide with an alkali metal halide (e.g. KF, KI) leads to replacement of the halogen via an SN2 Reaction. 

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