Structural chemistry of metal sulfides

The predominantly ionic alkali metal sulfides M2S (Li, Na, K, Rb, Cs) adopt the antifluorite structure (p. 118) in which each S atom is surrounded by a cube of 8 M and each M by a tetrahedron of S. The alkaline earth sulfides MS (Mg, Ca, Sr, Ba) adopt the NaCl-type 6 6 structure (p. 242) as do many other monosulfides of rather less basic metals (M = Pb, Mn, La, Ce, Pr, Nd, Sm, Eu, Tb, Ho, Th, U, Pu). However, many metals in the later transition element groups show substantial trends to increasing covalency leading either to lower coordination numbers or to layer-lattice structures. Thus MS (Be, Zn, Cd, Hg) adopt the 4 4 zinc blende structure (p. 1210) and ZnS, CdS and MnS also crystallize in the 4 4 wurtzite modification (p. 1210). In both of these structures both M and S are tetrahedrally coordinated, whereas PtS, which also has 4 4 

Greenwood, Ionic Crystals, Lattice Defects, and Nonstoichiometry, Chap. 3, pp. 37-61 also pp. 153-5, Butterworths, London, 1968. 

6 3 layer structure is the CdCl2-type adopted by TaS2, and the layer structures of M0S2 and WS2 are mentioned on p. 1018. 

Nominal formula Ratio Cr/S Proportion of sites occupied in alternate layers Random or ordered vacancies  

Finally, many disulfides have a quite different structure motif, being composed of infinite three-dimensional networks of M and discrete Sj units. The predominate structural types are pyrites, FeSa (also for M = Mn, Co, Ni, Ru, Os), and marcasite (known only for FeS2 among the disulfides). Pyrites can be described as a distorted NaCl-type structure in which the rodshaped S2 units (S-S 217 pm) are centred on the Cl positions but are oriented so that they are inclined away from the cubic axes. The marcasite structure is a variant of the rutile structure (Ti02, 

919- Many diselenides and ditellurides also adopt the Cdl2 structure and in some there is an almost continuous nonstoichiometric variation in 

---

Many of the most important naturally occurring minerals and ores of the metallic elements are sulfides (p. 648), and the recovery of metals from these ores is of major importance. Other metal sulfides, though they do not occur in nature, can be synthesized by a variety of preparative methods, and many have important physical or chemical properties which have led to their industrial production. Again, the solubility relations of metal sulfides in aqueous solution form the basis of the most widely used scheme of elementary qualitative analysis. These various more general considerations will be briefly discussed before the systematic structural chemistry of metal sulfides is summarized. 

D. J. Vaughan and J. R. Craig, Mineral Chemistry of Metal Sulfides, Cambridge University Press, Cambridge, 1978, 493 pp. A comprehensive account of the structure bonding and properties of mineral sulfides. 

Our knowledge concerning soluble metal complexes with sulfide ions as ligands has increased considerably during the last two decades and this kind of Compound is still of topical interest. Some of the reasons for this are the development of a very flexible and fascinating structural chemistry of multinuclear metal-sulfur complexes, the fact that the active sites of some electron transfer proteins contain metal ions and labile sulfur,41,42 and also the relation of metal-sulfur cluster compounds to some heterogeneous catalysts. In addition, apart from the numerous binary and ternary sulfides which occur in nature, we have at our disposal a rich solid state chemistry of metal sulfides, which has been reviewed elsewhere and will be excluded here.43"17... 

The platinum metal chalcogenides in general are easier to prepare than the corresponding oxides. Whereas special conditions of temperature and pressure are required to prepare many of the oxides, the platinum metals react most readily with S, Se, and Te. A number of additional differences concerning the chemistry of the chalcogenides and the oxides are summarized as follows The metal—sulfur (selenium, tellurium) bond has considerably more covalent character than the metal-oxygen bond and, therefore, there are important differences in the structure types of the compounds formed. Whereas there may be considerable similarity between oxides and fluorides, the structural chemistry of the sulfides tends to be more closely related to that of the chlorides. The latter compounds... 

The structural chemistry of the actinides is often similar to that of lighter transition metals, such as Zr and Hf, and to that of the lanthanides however, the diffuse nature of the 5/ orbitals leads to some differences and specifically to interesting magnetic and electrical properties. The actinide sulfides are generally isostructural with the selenides, but not with the analogous tellurides. The binary chalcogenides of uranium and thorium have been discussed in detail [66], but the structural... 

The reaction of carbonyl sulfide with [M(02)(PPh3)2] (where M = Pd or Pt) has resulted in the first reported examples of transition metal complexes of the monothiocarbonate anion (47 R = O-). Bidentate S—O coordination was concluded from 3IP H NMR analyses of these compounds.184 A short structural review of metal complexes of monothiocarbamate ions (47 R = N(R )R") demonstrates their varied coordination chemistry.185 In complexes of the dialkyl forms the sulfur atom is seen to have considerable mercaptide character , whereas aromatic amine derivatives demonstrate C—S and M—S partial multiple bonding.185,251 A review on the coordination chemistry of these ligands has appeared.186 Additional detail is provided in Chapter 16.4 of this volume. 

In general, most of doped or nanosized metal sulfide solid solutions could be synthesized by soft chemistry routes however, their low surface areas seriously limit the enhancements in activity. The preparation of high surface area samples with mesoporous stmctures and exposed surface sites is still a great challenge and highly desired [161]. At this end, research efforts should be directed at constructing 2D nanosheets and nanoporous structures of metal sulfide solid solutions [158,162-164]. In addition, the surface areas of metal sulfide solid solutions can be enhanced by loading them into the porous materials such as microporous and mesoporous silicas [165-167]. 

The planets nearest the Sun have a high-temperature surface while those further away have a low temperature. The temperature depends on the closeness to the Sun, but it also depends on the chemical composition and zone structures of the individual planets and their sizes. In this respect Earth is a somewhat peculiar planet, we do not know whether it is unique or not in that its core has remained very hot, mainly due to gravitic compression and radioactive decay of some unstable isotopes, and loss of core heat has been restricted by a poorly conducting mainly oxide mantle. This heat still contributes very considerably to the overall temperature of the Earth s surface. The hot core, some of it solid, is composed of metals, mainly iron, while the mantle is largely of molten oxidic rocks until the thin surface of solid rocks of many different compositions, such as silicates, sulfides and carbonates, occurs. This is usually called the crust, below the oceans, and forms the continents of today. Water and the atmosphere are reached in further outward succession. We shall describe the relevant chemistry in more detail later here, we are concerned first with the temperature gradient from the interior to the surface (Figure 1.2). The Earth s surface, i.e. the crust, the sea and the atmosphere, is of... 

A brief historical note on the structure of the iron-sulfur clusters in ferredoxins is relevant. After the first analytical results revealed the presence of (nearly) equimolar iron and acid-labile sulfur, it was clear that the metal center in ferredoxins did not resemble any previously characterized cofactor type. The early proposals for the Fe S center structure were based on a linear chain of iron atoms coordinated by bridging cysteines and inorganic sulfur (Blomstrom et al., 1964 Rabino-witz, 1971). While the later crystallographic analyses of HiPIP, PaFd, and model compounds (Herskovitz et al., 1972) demonstrated the cubane-type structure of the 4Fe 4S cluster, the original proposals have turned out to be somewhat prophetic. Linear chains of sulfide-linked irons are observed in 2Fe 2S ferredoxins and in the high-pH form of aconitase. Cysteines linked to several metal atoms are present in metallothionein. The chemistry of iron-sulfur clusters is rich and varied, and undoubtedly many other surprises await in the future. 

The main classes of materials employed as catalysts are metals (generally transition and noble metals), oxides (including transition-metal oxides), transition-metal sulfides and zeolites. In the following sections, we discuss some of the more common structures and chemistry exhibited by catalytic systems. 

Metal sulfides belong to the most important classes of compounds because they are of general significance for geochemistry (they are the most important ores for many metals), analytical and structural chemistry, and biochemistry (metal sulfide systems act as electron transfer systems) as well as catalysis (a high percentage of industrially used heterogeneous catalysts are sulfides) and materials science. 

Structure (1) explains the formation of sulfur and sulfite in the presence of acid structure (2) is consistent with the formation of sulfide and sulfate in the presence of heavy metals. The bonding in thiosulfate complexes and the chemistry of thiosulfates are normally explained on the basis of (2) (see also... 

Non-aqueous synthetic methods have recently been used to assemble mesoporous transition metal oxides and sulfides. This approach may afford greater control over the condensation-polymerization chemistry of precursor species and lead to enhanced surface area materials and well ordered structures [38, 39], For the first time, a rational synthesis of mesostructured metal germanium sulfides from the co-assembly of adamantanoid [Ge4S ()]4 cluster precursors was reported [38], Formamide was used as a solvent to co-assemble surfactant and adamantanoid clusters, while M2+/1+ transition metal ions were used to link the clusters (see Fig. 2.2). This produced exceptionally well-ordered mesostructured metal germanium sulfide materials, which could find application in detoxification of heavy metals, sensing of sulfurous vapors and the formation of semiconductor quantum anti-dot devices. 

---