S-, Se-, and

Chiral carbon atoms are common, but they are not the only possible centers of chirality. Other possible chiral tetravalent atoms are Si, Ge, Sn, N, S, and P, while potential trivalent chiral atoms, in which non-bonding electrons occupy the position of the fourth ligand, are N, P, As, Sb, S, Se, and Te. Furthermore, a center of chirality does not even have to be an atom, as shown in the structure represented in Figure 2-70b, where the center of chirality is at the center of the achiral skeleton of adamantane. 

Some amplification of the classification of heterocychc compounds may now be given. The two important hetero atoms are oxygen and nitrogen in the former class are included S, Se and Te and in the latter class P, As, etc. The sub-division (hetero-classes) of Division III is as follows ... 

Most striking colors are obtained in glasses containing 10—20 wt % K2O, 10—22 wt % ZnO, and 50—60 wt % silica. CaO and 2 3 present (6). To this batch is added 1—3 wt % CdS, CdSe, and/or CdTe. Melting must be under neutral or mildly reducing conditions. Otherwise, S, Se, and Te will be oxidized to SO2, Se02, or Te02, which are colorless. 

Figure 12 Plot of the Cu shake-up energies vs. the energy difference of the first two UV PES bands for aromatic (CH)4X (X = O, N, S, Se and Te)...

Oxidative Ring Closure Reactions 4.03.4.1.1 C—N bond formation N—N bond formation C—S bond formation N—S bond formation O—C bond formation O—N bond formation S—S, S—Se and Se—Se bond formation Electrophilic Ring Closures via Acylium Ions and Related Intermediates Ring Closures via Intramolecular Alkylations... 

Weak interactions may occur between molecules (intermolecular association) as well as within a molecule (intramolecular) for chalcogen-nitrogen ring systems. This behaviour is especially significant for odd electron species, e.g., [EsNa]" (4.14, E = S, Se) and [PhCNaEa] (4.15, E = S, Se), both of which are seven r-electron molecules. As mentioned in the previous section, it also occurs for the eight r-electron dithiatriazines 4.10... 

None of the three elements is particularly abundant in the earth s crust though several minerals contain them as major constituents. As can be seen from Table 13.1, arsenic occurs about halfway down the elements in order of abundance, grouped with several others near 2 ppm. Antimony has only one-tenth of this abundance and Bi, down by a further factor of 20 or more, is about as unabundant as several of the commoner platinum metals and gold. In common with all the post-transition-element metals. As, Sb and Bi are chalcophiles, i.e. they occur in association with the chalcogens S, Se and Te rather than as oxides and silicates. 

Lower formal oxidation states are stabilized, however, by M-M bonding in ternary chalcogenides such as M MeQn, M4M6Q13 (M = alkali metal M = Re, Tc Q = S, Se) and the recently reported M gMeS. Their structures are all based on the face-capped, octahedral MeXg cluster unit found in Chevrel phases (p. 1018) and in the dihalides of Mo and W... 

Coordination by halide ions is rather weak, that of especially so, but from non-aqueous solutions it is possible to isolate anionic complexes of the type [LnXg]. These are apparently, and unusually for Ln , 6-coordinate and octahedral. The heavier donor atoms S, Se, and As form only a few... 

Acylation of 3-arylamino-4-arylimino-4//-pyrido[l,2-u]pyrazines (373) with acyl chlorides afforded mixtures of mono- and bisacylated derivatives 374 and 375 (99JPR332). Acetyl chloride gave only monoacylated product 374 (R = 4-MePh, R =Me). Bis-acylated derivative 375 (R = 4-MePh, r = Me) was obtained in 68% yield in boiling toluene. Reaction of 373 with dienophiles 376 and 377 gave 4-thiono and 4-seleno derivatives of 4//-pyrido[l,2-u]pyrazines 378 (Y==S, Se) and 4-imino-4//-pyrido[l,2-u]pyrazines 379, respectively (99JPR332). 

Fig. 1. Chalcogenide halides in ternary systems having the components the Group IB elements Cu, Ag, and Au, the chalcogens S, Se, and Te, and the halogens Cl, Br, and I, They are indicated as M , Y, and X ", respectively. (Redrawn from A. Rabenau, H. Rau, and G. Rosenstein, J. Less-Common Metals 21, 395 (1970), Fig. 4, p. 401.)...

A systematic study of this class of compounds did not start until twenty years later and led to the preparation of a series of M3Q7X4 (M = Mo, W Q = S, Se and X = C1, Br) inorganic polymers by high-temperature reactions (ca. 350 °C) of the elements in a sealed tube [10-14]. The interest on these cluster phases was mainly motivated by their excellent role as synthons for the preparation of molecular M3Q7 and M3Q4 cluster complexes, as will be presented in this section. 

Eighteen isotopes of sulfur, 17 of selenium, 21 of tellurium, and 27 of polonium have been registered of these, 4 sulfur, 6 selenium, and 8 tellurium isotopes are stable, while there is no stable isotope of polonium. None of the naturally occurring isotopes of Se is radioactive its radioisotopes are by-products of the nuclear reactor and neutron activation technology. The naturally occurring, stable isotopes of S, Se, and Te are included in Table 1.2. 

Basic physical properties of sulfur, selenium, and tellurium are indicated in Table 1.3. Downward the sulfur sub-group, the metallic character increases from sulfur to polonium, so that whereas there exist various non-metallic allotropic states of elementary sulfur, only one allotropic form of selenium is (semi)metallic, and the (semi)metallic form of tellurium is the most common for this element. Polonium is a typical metal. Physically, this trend is reflected in the electrical properties of the elements oxygen and sulfur are insulators, selenium and tellurium behave as semiconductors, and polonium is a typical metallic conductor. The temperature coefficient of resistivity for S, Se, and Te is negative, which is usually considered... 

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