Platinum-ammonia compounds

One of the first important steps in unravelling the problem was taken by Berzelius with regard to ammonia compounds of the platinum salts. Reasoning from the duaiistic theory, he believed these substances to be complexes formed by the union of ammonia with another complex this complex was not decomposed on treatment with aeids, arul it did not affect the saturation capacity of the base. lie used formula of a special type to express the nature of the complex. Thus, the union of platinum chloride and ammonia was represented by... 

The availability of equipment to measure molar conductivity of solutions was turned to good use. It is interesting to note that coordination chemists still make use of physical methods heavily in their quest to assign structures - it s just that the extent and sophistication of instrumentation has grown enormously in a century. What conductivity could tell the early coordination chemist was some further information about the apparently ionic species inferred to exist through the silver ion precipitation reactions. This is best illustrated for a series of platinum(IV) complexes with various amounts of chloride ion and ammonia present (Figure 3.1). From comparison of measured molar conductivity with conductivities of known compounds, the number of ions present in each of the complexes could be determined. We now understand these results in terms of modern formulation of the complexes as octahedral platinum(IV) compounds with coordinated ammonia, where coordinated chloride ions make up any shortfall in the fixed coordination number of six. This leaves in most cases some free ionic chloride ions to balance the charge on the complex cation. 

Ammonium chloride in aqueous solution yields chlorine ions just as the platinum. chloride-ammonia compound, 2NH3.PtCl4 with 1, 2, 3, or 4 additional molecules of ammonia does. Since ionization was pointed out as a characteristic property determining in which way the ammonia had added to the platinic chloride or the influence it exerted in the compound, it is likely that the ammonia in the ammonium chloride is combined with the hydrogen chloride in the same way that the ammonia is combined with the platinic chloride when the chlorines of the latter become ionic. If, therefore, the structure of ammonium chloride is known, it is possible to assign a structure to the addition compounds of platinic chloride and ammonia as far as the ammonia molecules which cause the chlorine atoms to become ionic are concerned. 

Single-bond cleavage with molecular hydrogen is termed hydrogenolysis. Palladium is the best catalyst for this purpose, platinum is not useful. Desulfurizations are most efficiently per-formed with Raney nickel (with or without hydrogen G.R. Pettit, 1962 A or with alkali metals in liquid ammonia or amines. The scheme below summarizes some classes of compounds most susceptible to hydrogenolysis. 

Ammonia forms a great variety of addition or coordination compounds (qv), also called ammoniates, ia analogy with hydrates. Thus CaCl2 bNH and CuSO TNH are comparable to CaCl2 6H20 and CuSO 4H20, respectively, and, when regarded as coordination compounds, are called ammines and written as complexes, eg, [Cu(NH2)4]S04. The solubiHty ia water of such compounds is often quite different from the solubiHty of the parent salts. For example, silver chloride, AgQ., is almost iasoluble ia water, whereas [Ag(NH2)2]Cl is readily soluble. Thus silver chloride dissolves ia aqueous ammonia. Similar reactions take place with other water iasoluble silver and copper salts. Many ammines can be obtained ia a crystalline form, particularly those of cobalt, chromium, and platinum. 

The organic bases form, like ammonia, crystalline chloroplati-nates with platinic chloride of the general formula BoH,j,PtCl,). By estimating the amount of platinum present in the salt, it is possible to calculate the molecular weight of the platinum compound, and consequently that of the base. 

Platinum, palladium, and rhodium will function well under milder conditions and are especially useful when other reducible functions are present. Freifelder (23) considers rhodium-ammonia the system of choice when reducing -amino nitriles and certain )5-cyano ethers, compounds that undergo extensive hydrogenolysis under conditions necessary for base-metal catalysis. 

C and weighed. The precipitate is almost insoluble in hot water, but dissolves readily in ammonia and cyanide solutions. Gold is reduced to the metal by the reagent, and platinum (if present in appreciable quantity) is partially precipitated either as a greenish complex compound or as the metal, upon boiling the solution. The precipitation of palladium is not complete in the presence of nitrates. 

Several preparative methods do not use elemental mixtures. Group IIA-Pt intermetallic compounds have been prepared by reacting platinum metal with the group-IIA oxide under hydrogen or ammonia at 900-1200 C. Beryllium metal reacts with neptunium fluoride under vacuum at 1100-1200°C to form BC 3Np. 

Our investigations showed that in mixed melts of eutectic composition carbamide-NH4(K)Cl, the oxidation and reduction of melt constituents take place mainly independently of each other. The anodic process at platinum electrodes in the range of potentials below 0.9V is associated with the direct oxidation of carbamide to secondary and tertiary amide compounds, accumulation of ammonium ions in the melt, and evolution of the same gaseous products as in carbamide electrolysis [8], The cathodic process is accompanied by the formation of ammonia, CO, and C02, i.e. of the same products as in pure- carbamide electrolysis. In contrast to carbamide melt, a large amount of hydrogen appears in the cathode gases of the mixed melt, and in the anode gases of the carbamide-KCl melt, the presence of chlorine has been established at potentials above 0.9V. In the... 

Transition metals and their compounds are used as catalysts. Catalysts you may already know are Iron In the Haber process (Industrial production of ammonia) platinum in the Ostwald process (Industrial production of nitric acid) and platinum, rhodium and palladium In catalytic converters. 

Consequently, by choosing proper conditions, especially the ratios of the carbonyl compound to the amino compound, very good yields of the desired amines can be obtained [322, 953]. In catalytic hydrogenations alkylation of amines was also achieved by alcohols under the conditions when they may be dehydrogenated to the carbonyl compounds [803]. The reaction of aldehydes and ketones with ammonia and amines in the presence of hydrogen is carried out on catalysts platinum oxide [957], nickel [803, 958] or Raney nickel [956, 959,960]. Yields range from low (23-35%) to very high (93%). An alternative route is the use of complex borohydrides sodium borohydride [954], lithium cyanoborohydride [955] and sodium cyanoborohydride [103] in aqueous-alcoholic solutions of pH 5-8. 

In a review of explosions involving derivatives of gold, silver and platimmi, reactions of ammonia with gold and silver compoimds, and of hydrogen in presence of platinum compounds are emphasised. 

Forms a number of coordination compounds (ammonia complex) with several metals adds to AgCl forming soluble complex [Ag(NH3)2]Cl forms tetraamine complex [Cu(NH3)4]S04 with CUSO4 and forms many hexaamine complexes with cobalt, chromium, palladium, platinum and other metals. 

The importance of catalysts in chemical reactions cannot be overestimated. In the destruction of ozone previously mentioned, chlorine serves as a catalyst. Because of its detrimental effect to the environment, CFCs and other chlorine compounds have been banned internationally. Nearly every industrial chemical process is associated with numerous catalysts. These catalysts make the reactions commercially feasible, and chemists are continually searching for new catalysts. Some examples of important catalysts include iron, potassium oxide, and aluminum oxide in the Haber process to manufacture ammonia platinum and rhodium in the Ostwald synthesis of nitric... 

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