Transition Element Sulfides

Trialkyl- and triarylarsine sulfides have been prepared by several different methods. The reaction of sulfur with a tertiary arsine, with or without a solvent, gives the sulfides in almost quantitative yields. Another method involves the reaction of hydrogen sulfide with a tertiary arsine oxide, hydroxyhahde, or dihaloarsorane. X-ray diffraction studies of triphenylarsine sulfide [3937-40-4], C gH AsS, show the arsenic to be tetrahedral the arsenic—sulfur bond is a tme double bond (137). Triphenylarsine sulfide and trimethylarsine sulfide [38859-90-4], C H AsS, form a number of coordination compounds with salts of transition elements (138,139). Both trialkyl- and triarylarsine selenides have been reported. The trialkyl compounds have been prepared by refluxing trialkylarsines with selenium powder (140). The preparation of triphenylarsine selenide [65374-39-2], C gH AsSe, from dichlorotriphenylarsorane and hydrogen selenide has been reported (141), but other workers could not dupHcate this work (140). 

Transition elements, for which variable valency is energetically feasible, frequently show non-stoichiometric behaviour (variable composition) in their oxides, sulfides and related binary compounds. For small deviations from stoichiometry a thermodynamic approach is instructive, but for larger deviations structural considerations supervene, and the possibility of thermodynamically unstable but kinetically isolable phases must be considered. These ideas will be expanded in the following paragraphs but more detailed treatment must be sought elsewhere. " ... 

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... 

The magnetic criterion is particularly valuable because it provides a basis for differentiating sharply between essentially ionic and essentially electron-pair bonds Experimental data have as yet been obtained for only a few of the interesting compounds, but these indicate that oxides and fluorides of most metals are ionic. Electron-pair bonds are formed by most of the transition elements with sulfur, selenium, tellurium, phosphorus, arsenic and antimony, as in the sulfide minerals (pyrite, molybdenite, skutterudite, etc.). The halogens other than fluorine form electron-pair bonds with metals of the palladium and platinum groups and sometimes, but not always, with iron-group metals. 

Bence, A.E. (1983) Volcanogenic massive sulfides rtx k/water interactions in ba.saltic systems and their effects on the distribution of the rare earth elements and selected first. series transition elements (abst.). 4th International Symposium on Water-Rock interaction, Mi.sasa, Japan, 48. 

However, in sulphides and related minerals, the effects of covalent bonding predominate and orbital overlap must be taken into account. Thus, concepts of molecular orbital theory are described in chapter 11 and applied to aspects of the sulfide mineralogy of transition elements. Examples of computed energy diagrams for molecular clusters are also presented in chapter 11. There, it is noted that the fundamental 3d orbital energy splitting parameter of crystal field theory, A, receives a similar interpretation in the molecular orbital theory. 

Those in which the metal atoms are in somewhat higher oxidation states (+2 to +4) and the ligands are typically halide, sulfide, or oxide ions and some others of the same ilk as those in mononuclear Werner complexes. Clusters of this type are most common among the early transition elements, groups 5-7. 

Cd + can be detected by the insolubility of its yeUow sulfide (see Analytical Chemistry of the Transition Elements). Several reaction and spot tests allow the identification of Cd +. Quantitative determinations are based on gravimetric (CdS or /3-naphthylquinoltne complex) or titrimetric (EDTA) methods. Several physical techniques can be used in quantitative and qualitative analysis polarography (or related techniques, even in the presence of Zn, Cu, Bi and Pb), electrodeposition, colorimetric methods, flamephotometric methods, neutron activation, atomic absorption, and ICP spectrometry and ion selective electrodes. 

The second phase of transition element discovery involved those which could readily be released from minerals through heating or reduction by hot charcoal. Again copper in the carbonate mineral malachite, silver in the sulfide mineral argentite and mercury as the sulfide in cinnabar might... 

Factor-1 samples contain high concentrations of many trace elements, particularly boron and the transition elements Co, Cu, Mo, Ni, Pb, Zn, and V (Table III). These samples also contain illite (CR-2 core) and relatively high concentrations of analcime and oil (both cores) which suggests that adsorption of trace elements onto clay, altered tuffaceous material, and (or) organic matter may be important 1n controlling the distribution of these trace elements. The sulfide phase also may control the occurrence of these metals (10-11). Factor 1 samples also... 

Catalytically interesting semiconductors are oxides and sulfides of transition elements. " Unlike metals, electronic bands do not overlap but form separated regions, shown in Fig. 4.14. 

---