Sulfides block metal

Hydrogen sulfide dissolves in water to give a solution of hydrosulfuric acid that, as a result of its oxidation by dissolved air, slowly becomes cloudy as S8 molecules form and then coagulate. Hydrosulfuric acid is a weak diprotic acid and the parent acid of the hydrogen sulfides (which contain the HS ion) and the sulfides (which contain the S2 ion). The sulfides of the s-block elements are moderately soluble, whereas the sulfides of the heavy p- and d-block metals are generally very insoluble. 

FIGURE 21.2 Primary mineral sources of metals. The s-block metals occur as chlorides, silicates, and carbonates. The d- and p-block metals are found as oxides and sulfides, except for the group 3B metals, which occur as phosphates, and the platinum-group metals and gold, which occur in uncombined form. There is no mineral source of technetium (Tc in group 7B), a radioactive element that is made in nuclear reactors. 

We might also expect to find oxide ores for the s-block metals and sulfide ores for the more electronegative p-block metals. In fact, sulfide ores are common for the p-block metals, except for A1 and Sn, but oxides of the s-block metals are strongly basic and far too reactive to exist in an environment that contains acidic oxides such as CO2 and SiC>2. Consequently, s-block metals are found in nature as carbonates, as silicates, and, in the case of Na and K, as chlorides (Sections 6.7 and 6.8). Only gold and the platinum-group metals (Ru, Os, Rh, Ir, Pd, and Pt) are sufficiently unreactive to occur commonly in uncombined form as the free metals. 

Thiocarbamates and dithiocarbonates, which have attracted interest as possible sources of metal sulfides, are known with a variety of x-block metals, including lithium, calcium, ... 

Alkali sulfides transpose salts of the d- or p-block metals, e.g. ... 

Sulfides of 5 -block elements are moderately soluble in water, whereas the sulfides of the heavy p- and i/-block metals are generally very insoluble. 

The experiment conducted by Rutherford and his co-workers involved bombarding gold foil with alpha particles, which are doubly charged helium atoms. The apparatus used in their experiment is shown in Figure 14-9. The alpha particles are produced by the radioactive decay of radium, and a narrow beam of these particles emerges from a deep hole in a block of lead. The beam of particles is directed at a thin metal foil, approximately 10,000 atoms thick. The alpha particles are delected by the light they produce when they collide with scintilltaion screens, which are zinc sulfide-covered plates much like the front of the picture tube in a television set. The screen... 

A pure transition metal is best described by the band theory of solids, as introduced in Chapter 10. In this model, the valence s and d electrons form extended bands of orbitals that are delocalized over the entire network of metal atoms. These valence electrons are easily removed, so most elements In the d block react readily to form compounds oxides such as Fc2 O3, sulfides such as ZnS, and mineral salts such as zircon, ZrSi O4. ... 

Enantiomerically pure sulfoxides play an important role in asymmetric synthesis either as chiral building blocks or stereodirecting groups [156]. In the last years, metal- and enzyme-catalyzed asymmetric sulfoxidations have been developed for the preparation of optically active sulfoxides. Among the metal-catalyzed processes, the Kagan sulfoxidation [157] is the most efficient, in which the sulfide is enantioselectively oxidized by Ti(OzPr)4/tBuOOH in the presence of tartrate as chirality source. However, only alkyl aryl sulfides may be oxidized by this system in high enantiomeric excesses, and poor enantioselectivities were observed for dialkyl sulfides. 

Chiral sulfoxides have emerged as versatile building blocks and chiral auxiliaries in the asymmetric synthesis of pharmaceutical products. The asymmetric oxidation of prochiral sulfides with chiral metal complexes has become one of the most effective routes to obtain these chiral sulfoxides.We have recently developed a new heterogeneous catalytic system (WO3-30% H2O2) which efficiently catalyzes both the asymmetric oxidation of a variety of thioethers (1) and the kinetic resolution of racemic sulfoxides (3), when used in the presence of cinchona alkaloids such as hydroquinidine 2,5-diphenyl-4,6-pyrimidinediyl diether [(DHQD)2-PYR], Optically active sulfoxides (2) are produced in high yields and with good enantioselectivities (Figure 9.3). ... 

The reaction is of great value and most of the early work in the field is quoted and discussed in [203] by Block. As the allyl vinyl sulfide can be metallated and submitted to electrophilic substitution prior to rearrangement and the thiocarbonyl group hydrolysed in situ to a carbonyl group in the reaction product, the process has found considerable utility. The syntheses of propylure [488] and ris-jasmone [489] are early examples in which a thioaldehyde was intermediary formed (Y = H). A thioketone was involved [490] in the rearrangement of the allyl allenyl sulfide shown here. 

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