Valence chalcogenides

All three elements combine readily with most metals and many non-metals to form binary chalcogenides. Indeed, selenides and tellurides are the most common mineral forms of these elements (p. 748). Nonstoichiometry abounds, particularly for compounds with the transition elements (where electronegativity differences are minimal and variable valency is favoured), and many of the chalcogenides can be considered... 

Solid-state cluster chemistry is dominated by octahedral (M 5L8)L6 and (MsLi2)L units which are the focus of this paper. These two cluster types are different in the way the metal octahedral core is surrounded by the ligands. In (MsLg)L6-type clusters (Fig. 6.1a), typical for molybdenum and rhenium halides, chalcogenides, and chalcohalides, eight innei hgands (L ) cap the octahedron faces and six outer ligands (L ) are located in the apical positions [9]. For metals with a smaller number of valence electrons, the (M6L i2)L -type clusters... 

Examples of known ternary (and quaternary) chalcogenide compounds, classified according to a formal valence combination scheme, are given in Table 1.4. These compounds were collected from a compilation of Madelung [40] regarding semiconductor materials. To be sure, numerous other systems exist. Some important ternary compounds or classes will be considered in the relevant sections of the present chapter. 

Ni3Sn2S2 Valence states of nickel, tin, and sulfur in the ternary chalcogenide, and " Sn Mossbauer investigations, XPS and band structure calculations... 

The situation is very similar in the Chevrel phases. These are ternary molybdenum chalcogenides A,.[Mo6Xg] (A = metal, X = S, Se) that have attracted much attention because of their physical properties, especially as superconductors. The parent compound is PbMo6Sg it contains Mo6Sg clusters that are linked with each other in such a way that the free coordination sites of one cluster are occupied by sulfur atoms of adjacent clusters (Fig. 13.9). The electric properties of Chevrel phases depend on the number of valence electrons. With 24 electrons per cluster (one electron pair for each edge of the... 

If you move left one column in the periodic table from the halides, the chalcogenides need two electrons to complete their valence shell, and thus can bond to the surface and each other simultaneously. This appears to account for much of the interesting surface chemistry of chalcogenide atomic layers. Chalcogenides, including oxides (corrosion), are some of the most studied systems in surface chemistry. The oxides are clearly the most important, but significant amounts of work have been done with sulfur, selenium and tellurium. 

Trends in the electronic structure of the chalcogenide catalysts have proved to be helpful in the design and understanding of the catalyst clusters. During ORR, the molecular oxygen has been found to react with the cluster as a whole, rather than individual metal atoms.177 The overall number of electrons per cluster unit (NEC) in the valence bond has been shown to have a factor in the activity and stability of the cluster catalysts.177,181 The unsubstituted Chevrel phases have a NEC of 20.177,181 Substituting or intercalating other transition metals into the crystal lattice to make ternary or pseudo-binary Chevrel phases allows for the increase of NEC. It has been found that as the NEC approaches 24, the catalytic activity improves.181 Alonso-Vante compiled the results from his previous studies to show the effect of NEC in... 

Chalcogenides, 5 94-96 berkelium, 28 49, 53-54 lattice energies of, 1 192, 193 ligands, 45 16 Chalcogen(II) compounds binary halides, 35 274—280 complexes with Lewis bases, 35 293-295 halo-chalcogenates(ll), 35 280-288 mixed-valence compounds, 35 288-293 cationic species, 35 291-293... 

Adams, St. (2001). Relationship between bond valence and bond softness of alkali halides and chalcogenides. Acta Cryst. B57, 278 -87. 

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