Platinum reaction with sulfides

An unusual sulfide complex of platinum(II) is obtained with electron-rich alkenes (equation 517). These alkenes are often carbene precursors (Section 52.4), but the reaction with Pt2Cl2(/i-Cl)2(PEt3)2 gives a sulfide complex (188).1738 With the compound (MeS)2C=C(SMe)2, the chelate complex (189) is formed with platinum(H), but with platinum(IV) the ligand will bridge two platinums (190).1739... 

For both the dipalladium and palladium-platinum complexes the metal-metal bond is unusually reactive and a number of small molecules undergo an insertion reaction with (9) to give (10 equation 8). The corresponding sulfide-bridged dipalladium dimer can be prepared from the reaction of S8 or MeCHCH2S with (9).83 A mixed rhodium-palladium dimer can also be prepared from (9) (see Scheme 6).84... 

Bulk aluminum may undergo the following dangerous interactions exothermic reaction with butanol, methanol, 2-propanol, or other alcohols, sodium hydroxide to release explosive hydrogen gas. Reaction with diborane forms pyrophoric product. Ignition on contact with niobium oxide + sulfur. Explosive reaction with molten metal oxides, oxosalts (nitrates, sulfates), sulfides, and sodium carbonate. Reaction with arsenic trioxide + sodium arsenate + sodium hydroxide produces the toxic arsine gas. Violent reaction with chlorine trifluoride, Incandescent reaction with formic acid. Potentially violent alloy formation with palladium, platinum at mp of Al, 600°C. Vigorous dissolution reaction in... 

All these photocorrosion processes are, of course, undesirable and it is obvious that their relative importance depends strongly on the presence of surface states which may facilitate recombination or redox reactions with adsorbed substrates. It is well known from ESR [69, 70, 94] and emission spectra [94] that most of these metal sulfide powders contain surface states. They are introduced during preparation of the powder as a result of lattice defects [72, 96], trapped holes [94], surface impurities [97] and metallization [38], and during the actual catalytic reaction as a consequence of irradiation and substrate adsorption. The stabilizing effect of plati-nization is exemplified by Figure 6 for the ZnS-catalyzed reduction of water in the presence of sodium formate [98]. Note that platinum does not accelerate the reaction but doubles the time of constant catalytic activity from 1 to 2 days. Similarly, the apparent product quantum yield of the 2,5-DHF dehydrodimerization is not increased but slightly decreases when platinizes ZnS is the photocatalyst [97]. 

A number of relevant review articles have appeared. Their subjects include the chemistry of antitumor platinum complexes, complexes of platinum metals with weak donor ligands, and transition metal complexes of sulfide, selenide, and telluride ligands (which includes much material on square-planar compounds). A review by Chanon and Tobe " on electron transfer catalysis relates to many reaction types, including ligand replacements at square planes. 

The equilibrium is more favorable to acetone at higher temperatures. At 325°C 97% conversion is theoretically possible. The kinetics of the reaction has been studied (23). A large number of catalysts have been investigated, including copper, silver, platinum, and palladium metals, as well as sulfides of transition metals of groups 4, 5, and 6 of the periodic table. These catalysts are made with inert supports and are used at 400—600°C (24). Lower temperature reactions (315—482°C) have been successhiUy conducted using 2inc oxide-zirconium oxide combinations (25), and combinations of copper-chromium oxide and of copper and silicon dioxide (26). 

Aromatic amine-Ketone. The interaction between anihne, the simplest of the aromatic amines with acetone in the presence of various catalysts to yield N-isopropylaniline was examined (Table 17.3). Among the catalysts tested, sulfided platinum catalysts were found to be the most active catalysts for this reaction. 

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