Tellurium trihalides preparation

Aryltellurium trichlorides 5 (R = aryl, X = Cl) are usually yellow, very stable crystalline solids, with a slight odor of hydrochloric acid, which probably arises from the reaction of 5 with the air moisture. Contact of 5 with metallic spatulas, with moist solvents, or prolonged exposure to light must be avoided. These compounds, however, can be handled in the air with no risk of decomposition. Aryltellurium tribromides (5, R = aryl, X = Br) are yellow crystalline solids, and the triiodides (5, R = aryl, X = 1) are dark red solids. The aryltellurium tribromides and triiodides were less explored for synthetic purposes, in contrast to the aryltellurium trichlorides, which were frequently used in several synthetic transformations. The aliphatic tellurium trihalides are less stable than the aromatic ones and were much less studied and used for preparative purposes. 

Organic tellurium compounds with one Te—C bond containing divalent, tetravalent, or hexavalent tellurium have been prepared. The most widely investigated and best characterized compounds are the diorgano ditellurium derivatives and the organo tellurium trihalides. Pentafluoroethyl tellurium chloride tetrafluoride is the only known example of a hexavalent tellurium compound with one Te-C bond in the molecule. 

Aryl tellurium bromides and iodides can be obtained by reaction of diaryl ditellurium compounds with an equimolar amount of bromine or iodine, when the solvent is able to dissolve the starting materials but not the aryl tellurium halide. The precipitation of the aryl tellurium halide prevents it from being converted to aryl tellurium trihalides. The aryl tellurium halides thus far isolated and suitable reaction media for their preparation are listed in Table 3 (p. 240). 

The possibility of preparing aryl tellurium halides from equimolar amounts of diaryl ditellurium compounds and aryl tellurium trihalides has hardly been explored. Only phenyl tellurium iodide and 2-biphenylyl tellurium bromide could be obtained by this route. The other aryl tellurium halides (including 3,4-dimethoxyphenyl tellurium chloride) decomposed under the reaction conditions to give diaryl tellurium dihalides and tellurium5. 

The reduction of alkyl tellurium trihalides is a convenient method for the preparation of the corresponding dialkyl ditellurium when the trihalides can be obtained by reactions other than the halogenolysis of the dialkyl ditellurium. Addition of tellurium tetrachloride to olefins and condensation with ketones produces alkyl tellurium trichlorides. Sodium sulfide nonahydrate4 and sodium or potassium disulfite5 8 were used as reducing agents. 

Organo tellurium trifluorides, trichlorides, tribromides, and triiodides are known. Aryl tellurium trihalides are generally more stable than alkyl tellurium trihalides. The sensitivity toward atmospheric agents decreases from the trichlorides to the triiodides. Very few organo tellurium trifluorides have been prepared and little is known about their reactivity. The general reactivity of aryl tellurium trihalides decreases from the chlorides to the iodides. 2-Chloroalkyl tellurium trichlorides, products of the addition of tellurium... 

The halogenolysis of dialkyl ditellurium compounds is a convenient method for the preparation of alkyl tellurium trihalides because dialkyl ditellurium compounds are easily accessible through alkylation of disodium ditelluride (p. 258). Diaryl ditellurium compounds generally obtained via reduction of organo tellurium trichlorides (p. 274), serve as starting materials for the syntheses of aryl tellurium tribromides and triiodides (Vol. IX, p. 1156) that are not obtainable from the hydrocarbons and tellurium telrabromide or tetraiodide. 

Alkyl tellurium halides, RTeX, in general, have no importance as starting materials for the preparation of alkyl tellurium trihalides. The alkyl tellurium halides are synthesized from dialkyl ditellurium compounds and elemental halogens. When alkyl tellurium trihalides are the desired products, there is no reason to prepare the monohalides first. However, when the tellurium monohalide is formed during the introduction of tellurium into an organic molecule, the reaction of this primary product with halogens is the method of choice for the preparation of the tellurium trihalides. This situation is realized for 3-oxo-l-propen-l-yl tellurium halides2,3. 

Oxo-1-propen-1-yl tellurium iodides did not react with iodine. The attempt to prepare mixed (chloride, bromide) tellurium trihalides was unsuccessful a mixture of trichlorides and tribromides was formed. When 1,3-diphenyl-3-oxo-l -propen-l-yl tellurium iodide was reacted with bromine, the bromide and elemental iodine were the only observed products. The 3-oxo-l-propen-l-yl tellurium trihalides are thermally unstable they decompose on mild heating to the tellurium halide and elemental halogen1. 

The Schiff base prepared from 2-formylphenyl butyl tellurium and 1,2-diaminoethane was converted to tellurium trihalides by excess sulfuryl chloride or bromine2. 

Tropylium aryltetrahalotellurates can be prepared from tropylium bromide and an aryl tellurium trihalide. A more convenient procedure avoiding the laborious preparation of the tropylium bromide uses cycloheptatricne and triphenylmethyl perchlorate2. The product of this reaction can then be converted to the tetrahalotellurate by treatment with hydrohalic acids. 

Diorgano tellurium dihalides are often the primary products of reactions producing compounds with two tellurium-carbon bonds. Such reactions arc the condensation of tellurium tetrachloride with aromatic compounds (p. 527), the addition of tellurium tetrachloride or organo tellurium trichlorides to carbon-carbon multiple bonds (p. 530, 544), and the alkylation or arylation of organo tellurium trihalides (p. 549). The symmetrical and unsymmetrical diorgano tellurium dihalides are convenient starting materials for the preparation of diorgano tellurium derivatives. 

Diaryl ditellurium compounds and aryl tellurium trihalides react in refluxing 1,2-dichloroethane to form diaryl tellurium dihalides and tellurium. The reactions are postulated to proceed via aryl tellurium halides that disproportionate into tellurium and diaryl tellurium dihalides. All reactions of this type thus far carried out on a preparative scale used pairs of reagents with the same aryl group2. 

Similarly prepared were the following r/-ani-2-alkoxycycloalkyl tellurium trihalides. ... 

Aryl tellurium trichlorides and N-, S-, or 0-donor ligands form 1 1 complexes when the components are combined in an organic solvent. Several complexes with a 1 2 stoichiometry and one complex with a 1 4 stoichiometry were also prepared. The few complexes of alkyl tellurium trihalides that are reported in the literature all have 1 1 stoichiometry The following organic compounds served as ligands. ... 

Halogen exchange reactions may be used to prepare tetrahalotellurates(IV) that are not accessible through reactions of aryl tellurium trihalides and onium halides. Treatment of tetrachloro- or bromotrichlorotellurates with dilute hydrobromic acid produces the tetrabromotellurates. The conversion of bromotellurates to tetrachlorotellurates requires concentrated hydrochloric acid. Chlorine and bromine are easily replaced by iodine when the tellurates are reacted with excess potassium iodide in dilute hydrochloric acid. The iodotellurates cannot be converted to the bromo- or chlorotellurates ... 

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