Chalcogenide halide compounds

Chemical shifts, in NMR, 4 234-245 Chemical transport reactions, and synthesis of chalcogenide halide compounds, 23 330-332. 364, 368-369... 

Elastic-inelastic collision model, Szilard-Chalmers reaction and, 1 269 Electrical conduction, in organic superconductors, 29 278-286 Electrical conductivity of chalcogenide halide compounds, 23 331 of Group IB, 23 337-339, 342, 346-349 photoelectric effects, 23 368, 410 semiconductors, 23 368, 390, 395-396, 400-402, 410-412 superconductors, 23 375-377 of graphite intercalation compounds, 23 290, 294, 309-310, 312, 317-318 Electric discharges arc type, 6 146-147 chemical reactions in, 6 189-191 chemical reactions in, 6 143-206... 

NMR spectra heteronuclear gold cluster compounds, 39 345-348 Phalaris canariensis esophageal cancer, 36 144-145 scanning proton microprobe, 36 149 structural motifs of silicas, 36 146 Pharmaceuticals, 18 177 Phase transitions, in chalcogenide halide compounds, 23 332, 408, 412 [PhCHjMejNAlHjlj, 41 225-226 [(PhCH2)jNLi]3 molecular structure, 37 94, 96 in solution, 37 107-108... 

Despite the tremendous amount of work on the binary compounds, copper chalcogenide halides were first reported in 1969 (304). Nine compounds of selenium and tellurium have been found, and they are listed in Table 1. Copper sulfide halides are still unknown. 

The most important mercury chalcogenide halides are of the type HgaYjXj (Y = S, Se, Te X = Cl, Br, I). The corresponding sulfide halides have been known for over 150 years (326). Quite a lot of work has been performed concerning the preparation, structures, electronic and optical properties, and phototropic behavior of these compounds. Mercury chalcogenide halides of other compositions have been mentioned in the literature (141). As most of these compounds are not well established, they will not be treated in detail, with the exception of the latest contributions (see Table V). 

Very little is known about chalcogenide halides of Group IVB elements. Although the existence of sulfide chlorides (45, 274, 329, 365) and of a selenide chloride (329) of titanium was claimed in early publications, their true composition, and even their existence, remains doubtful. They have usually been obtained by the reaction of titanium chlorides with sulfur and selenium, respectively, or with hydrogen sulfide. The synthesis of a pure compound, TiSClj, was published in 1959 (113). It is an intermediate of the reaction of TiCU with HjS. 

Although not yet published in a journal, according to thesis work, the vanadium compounds VSCl (11), VSBr, and VSI (208) seem to exist. Numerous niobium chalcogenide halides have been reported, and among these are the best characterized examples of Group VB (see Table X). Only two tantalum compounds, TaSjCU (361) and TaSCls (13) have thus far been described in the literature. 

Just as, in Group VB, niobium, so, in this Group, molybdenum provides most of the examples of the chalcogenide halides. The occurrence and preparation of such compounds are described in numerous publications. In most cases, they have been obtained as powders, with the composition based on chemical analyses only. The presence of defined, homogeneous phases is, therefore, in many cases doubtful. In addition, some published results are contradictory. A decision is possible where a complete structure analysis has been made. As will be shown later, the formation of metal-metal bonds (so-called clusters), as in the case of niobium, is the most characteristic building-principle. Such clusters... 

Only two compounds, W2S7CI8 (362) and W4S9CI6 (97) are mentioned in the older literature, their true nature being uncertain. The existence of the other compounds in Table XV seems to be well established. All of them were reported by the same group, and, with few exceptions, it remains the only work (57, 58, 131). This example illustrates that the lack of information on chalcogenide halides, especially of transition elements, has its main origin in the lack of systematic investigations. 

All of the known rhenium chalcogenide halides are stable in air. With the exception of RegSgCU, they are insoluble in water, acids, and the common organic solvents. They dissolve readily in hot, 50% KOH (263, 264). Re2S3Cl4 is soluble in water, and ethanol, but insoluble in nonpolar organic solvents. With acids, alkalis, or hot water, hydrolytic decomposition takes place. Alkaline solutions can be oxidized to produce perrhenate compounds. 

The structures of the rhenium chalcogenide halides have not been studied. X-Ray powder data were collected, in order to prove the homogeneity of the compounds 140, 263, 264, 353). 

Thiele and co-workers, who tried to prepare platinum chalcogenide halides, could neither isolate nor identify any pure, homogeneous compound (389). 

The gallium chalcogenide halides are hygroscopic compounds that decompose (without melting) at temperatures between 240 and 380°C to a mixture of chalcogenide and halide (see Table XVIII). The tel-luride halides are yellow, and the other compounds are colorless 160, 165). 

Again, the complete series of InYX compounds (Y = S,Se,Te X = Cl,Br,I) exists. Of the Group IIIA chalcogenide halides, the indium compounds have been the most extensively studied. 

The first chalcogenide halides of tin were reported in 1963 24). Although numerous publications since then have been devoted to this subject, the existence and true composition of some the compounds described here still seem questionable. It is, therefore, advisable to start with a discussion of the systems SnY-SnXji Y = S, Se, Te X = Cl, Br, I). 

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