Ammine

In spite of such resemblances, however, it is important to note that there are also significant differences between ammines and hydrates. One of these differences is implicit in what we have already said, for we find that in many cases ammines have simpler structures than the corresponding hydrates, owing to the less polar character of the ammonia in comparison with water. Thus although Mg(NH3)6Cl2 has the fluorite structure, this arrangement is not found in Mg(H20)6Cl2 because it is inconsistent with the tetrahedral form of the water molecule. 

A second difference between ammines and hydrates, again arising from the small dipole moment of the ammonia molecule, is that strong bonds cannot be formed between these molecules they are therefore found in ammines only in a co-ordinating and never in a structural capacity. For this reason the ammine counterparts of hydrates with an odd number of water molecules do not exist, and it is interesting to note, as an example of this point, that cupric sulphate forms only the hydrated ammine Cu(NH3)4S04. H20 and not the compound Cu(NH3)4S04. NH3. 

The structures of the metallic elements have already been described in chapters 5 and 7. We now turn to consider systems in which these elements are found in association as alloys. 

Alloy systems have been known to man since the Bronze Age. It is, however, only in recent times that they have been the subject of systematic studies, and in these studies no tool has proved more powerful than the technique of crystal structure analysis. Indeed, the extension of our knowledge and understanding of the properties of intermetallic systems to which it has given rise is one of the greatest achievements of crystal chemistry. Prior to the application of X-ray methods, the investigation of the properties of alloy systems was confined principally to observations of their behaviour in the liquid state, and the behaviour of the metal as a solid could be determined only by inference from these observations. Transitions in the solid state and the effect of mechanical or heat treatment could not, of course, be observed in this way, and for information on these properties the microscope and other purely physical methods had to be invoked. Even so, these methods were all more or less indirect, and it is only since the application of X-ray analysis that it has been possible to investigate directly in the solid state, under the precise conditions which are of technical interest and without damage to the specimen, the exact positions of all the atoms in the structure, and so to refer to their ultimate cause the physical and chemical properties of the alloy. 

It is not surprising that the application of such a powerful method of investigation should have led, on the experimental side, to a vast extension of our knowledge of the properties of alloy systems. Even more important, however, is the fact that it has also laid the foundations of the modem theory of the metallic state, for, as we have seen in chapter 5, the basic concept on which this theory is based is that of the periodic field in a crystal structure. The development of metallurgy in the past has been hampered by attempts to make metal systems conform to the laws of chemical combination established by observations on bodies in which forces of an entirely different character are operative. Alloys differ profoundly in many of their properties from 

Jonas and B. Norden, Inorg. Nuclear Chem. Letters, 1976,12, 43. 

Mentasi, E. Pelizzetti, and G. Girandi, J. Inorg. Nuclear Chem., 1976,38, 795. 

Diamines. Chromatography has been used to isolate three isomers of trans- and cis-[Co(CN)2 (RR)-cyclohexane-l,2-diamine 2] and five isomers of the corresponding propylenediamine complexes. Mer- and /ac-isomers of tris(meso-pentane-3,4-diamine)cobalt(iii) have been prepared and separated using column chromatography. The rates of aquation of three isomers of [CoCl(tmd)(dien)] and one isomer of [CoCl(tmdXdpt)] have been measured and the kinetic parameters calculated [dpt = NH2(CH2)3NH(CH2)3NH2, tmd = NH2(CH2)3NH2]. The interaction of [Co(dien)2] with sulphate, thiosulphate, sulphite, selenite, tellurite, and carbonate ions has been studied potentiometrically and stability constants determined for the outer-sphere complexes. The i.r. spectrum of octahedral 

Yamaneka, K. Saito, N. Komatsu, N. Hamada, H. Nishikawa, and M. Shibata, Bull. Chem. Soc. Japan, 1975, 48, 3631. 

Sakaguchi, S. Yamaznki, and H. Yoneda, Bull. Chem. Soc. Jepan, 1976,4B, 402. 

The only known symmetrical molecules of tlie type a2N-Na2 with single N-N bonds are those of hydrazine, N2H4, and dinitrogen tetrafluoride, N2F4. In some molecules in which O atoms are attached to N as, for example, nitramine, (a), 

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When naming complex ions the number and type of ligands is written first, followed by the name of the central metal ion. If the complex as a whole has a positive charge, i.e. a cation, the name of the central metal is written unchanged and followed by the oxidation state of the metal in brackets, for example [Cu(N 113)4] becomes tetra-ammine copper(II). A similar procedure is followed for anions but the suffix -ate is added to the central metal ion some examples are ... 

Aqueous ammonia can also behave as a weak base giving hydroxide ions in solution. However, addition of aqueous ammonia to a solution of a cation which normally forms an insoluble hydroxide may not always precipitate the latter, because (a) the ammonia may form a complex ammine with the cation and (b) because the concentration of hydroxide ions available in aqueous ammonia may be insufficient to exceed the solubility product of the cation hydroxide. Effects (a) and (b) may operate simultaneously. The hydroxyl ion concentration of aqueous ammonia can be further reduced by the addition of ammonium chloride hence this mixture can be used to precipitate the hydroxides of, for example, aluminium and chrom-ium(III) but not nickel(II) or cobalt(II). 

Because of ammine formation, when ammonia solution is added slowly to a metal ion in solution, the hydroxide may first be precipitated and then redissolve when excess ammonia solution is added this is due to the formation of a complex ammine ion, for example with copper(II) and nickel(II) salts in aqueous solution. 

In its chemistry, cadmium exhibits exclusively the oxidation state + 2 in both ionic and covalent compounds. The hydroxide is soluble in acids to give cadmium(II) salts, and slightly soluble in concentrated alkali where hydroxocadmiates are probably formed it is therefore slightly amphoteric. It is also soluble in ammonia to give ammines, for example Of the halides, cadmium-... 

Neutral and Cationic Ligands. Neutral and cationic ligands are used without change in name and are set off with enclosing marks. Water and ammonia, as neutral ligands, are called aqua and ammine, respectively. The groups NO and CO, when linked directly to a metal atom, are called nitrosyl and carbonyl, respectively. 

As an example, the entries in Table 8.12 for the zinc ammine complexes represent these equilibria ... 

Tabie 11.35 Cumuiative Formation Constants of Ammine Compiexes at 20°C,... 

Direct Titrations. The most convenient and simplest manner is the measured addition of a standard chelon solution to the sample solution (brought to the proper conditions of pH, buffer, etc.) until the metal ion is stoichiometrically chelated. Auxiliary complexing agents such as citrate, tartrate, or triethanolamine are added, if necessary, to prevent the precipitation of metal hydroxides or basic salts at the optimum pH for titration. Eor example, tartrate is added in the direct titration of lead. If a pH range of 9 to 10 is suitable, a buffer of ammonia and ammonium chloride is often added in relatively concentrated form, both to adjust the pH and to supply ammonia as an auxiliary complexing agent for those metal ions which form ammine complexes. A few metals, notably iron(III), bismuth, and thorium, are titrated in acid solution. 

TABLE 11.35 Cumulative Formation Constants of Ammine Complexes at 20°C, Ionic Strength 0.1 ... 

Nickel and cobalt are recovered by processes that employ both pressure leaching and precipitation steps. The raw materials for these processes can be sulfide concentrates, matte, arsenide concentrates, and precipitated sulfides. Typically, acidic conditions are used for leaching however, ammonia is also effective in leach solutions because of the tendency for soluble cobalt and nickel ammines to form under the leach conditions. 

Dispersed Metals. Bifimctional zeoHte catalysts, principally zeoHte Y, are used in commercial processes such as hydrocracking. These are acidic zeoHtes containing dispersed metals such as platinum or palladium. The metals are introduced by cation exchange of the ammine complexes, foUowed by a reductive decomposition (21) ... 

Simple nickel salts form ammine and other coordination complexes (see Coordination compounds). The octahedral configuration, in which nickel has a coordination number (CN) of 6, is the most common stmctural form. The square-planar and tetrahedral configurations (11), iu which nickel has a coordination number of 4, are less common. Generally, the latter group tends to be reddish brown. The 5-coordinate square pyramid configuration is also quite common. These materials tend to be darker in color and mostiy green (12). 

Ma.nufa.cture. Nickel carbonyl can be prepared by the direct combination of carbon monoxide and metallic nickel (77). The presence of sulfur, the surface area, and the surface activity of the nickel affect the formation of nickel carbonyl (78). The thermodynamics of formation and reaction are documented (79). Two commercial processes are used for large-scale production (80). An atmospheric method, whereby carbon monoxide is passed over nickel sulfide and freshly reduced nickel metal, is used in the United Kingdom to produce pure nickel carbonyl (81). The second method, used in Canada, involves high pressure CO in the formation of iron and nickel carbonyls the two are separated by distillation (81). Very high pressure CO is required for the formation of cobalt carbonyl and a method has been described where the mixed carbonyls are scmbbed with ammonia or an amine and the cobalt is extracted as the ammine carbonyl (82). A discontinued commercial process in the United States involved the reaction of carbon monoxide with nickel sulfate solution. 

Coordination Compounds. A large number of indium complexes with nitrogen ligands have been isolated, particularly where Ir is in the +3 oxidation state. Examples of ammine complexes include pr(NH3)3] " [24669-15-6], prCl(NH3)] " [29589-09-1], and / j -pr(03SCF3)2(en)2]" [90065-94-4], Compounds of A/-heterocychc ligands include trans- [xCX py)][ [24952-67-8], Pr(bipy)3] " [16788-86-6], and an unusual C-metalated bipyridine complex, Pr(bipy)2(C, N-bipy)] [87137-18-6]. Isolation of this latter complex produced some confusion regarding the chemical and physical properties of Pr(bipy)3]3+ (167). 

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. 

Cobalt exists in the +2 or +3 valence states for the majority of its compounds and complexes. A multitude of complexes of the cobalt(III) ion [22541-63-5] exist, but few stable simple salts are known (2). Werner s discovery and detailed studies of the cobalt(III) ammine complexes contributed gready to modem coordination chemistry and understanding of ligand exchange (3). Octahedral stereochemistries are the most common for the cobalt(II) ion [22541-53-3] as well as for cobalt(III). Cobalt(II) forms numerous simple compounds and complexes, most of which are octahedral or tetrahedral in nature cobalt(II) forms more tetrahedral complexes than other transition-metal ions. Because of the small stabiUty difference between octahedral and tetrahedral complexes of cobalt(II), both can be found in equiUbrium for a number of complexes. Typically, octahedral cobalt(II) salts and complexes are pink to brownish red most of the tetrahedral Co(II) species are blue (see Coordination compounds). 

Copper hydroxide is almost iasoluble ia water (3 p.g/L) but readily dissolves ia mineral acids and ammonia forming salt solutions or copper ammine complexes. The hydroxide is somewhat amphoteric dissolving ia excess sodium hydroxide solutioa to form ttihydroxycuprate [37830-77-6] [Cu(011)3] and tetrahydroxycuprate [17949-75-6] [Cu(OH) ]. ... 

Compounds of Tl have many similarities to those of the alkali metals TIOH is very soluble and is a strong base TI2CO3 is also soluble and resembles the corresponding Na and K compounds Tl forms colourless, well-crystallized salts of many oxoacids, and these tend to be anhydrous like those of the similarly sized Rb and Cs Tl salts of weak acids have a basic reaction in aqueous solution as a result of hydrolysis Tl forms polysulfldes (e.g. TI2S3) and polyiodides, etc. In other respects Tl resembles the more highly polarizing ion Ag+, e.g. in the colour and insolubility of its chromate, sulfide, arsenate and halides (except F), though it does not form ammine complexes in aqueous solution and its azide is not explosive. 

Solvates are perhaps less prevalent in compounds prepared from liquid ammonia solutions than are hydrates precipitated from aqueous systems, but large numbers of ammines are known, and their study formed the basis of Werner s theory of coordination compounds (1891-5). Frequently, however, solvolysis (ammonolysis) occurs (cf. hydrolysis). Examples are ... 

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