Metal ammines

Figure 4.34 shows the form of the interacting metal and ligand NHOs and the final own NBO for H4W(NH3), n = 1. (Corresponding plots for n = 2 and 3 are very similar.) The complementary lock-and-key overlap of the donor and acceptor hybrids is apparent in Fig. 4.34(a). The localized ammine— metal (nL nM ) interaction depicted in Fig. 4.34(a) is representative of sigma donation in a large number of metal-ligand complexes. 

Figure 4.35 Leading hyperconjugative donor-acceptor interactions between am-mine ligand and amminated metal fragment in H2W(NH3)2 cf. Fig. 4.33(b).

Powder reflectance spectra have shown that PCl5,CrCl3 involves an octahedral CrClg chromophore. The preparation, unit cells, and vibrational spectra of the hexa-ammine metal(iii) salts [M(NH3)g][CrCl6] (M = Cr, Co, or Rh) have been reported. ... 

Let s begin by recalling the successive formation constants of some ammine-metal complexes (Table 35.1). They govern the following equilibria ... 

But when an excess of ammonia is added, the precipitate dissolves essentially by formation of the diamminesilver(I) [Ag(NH3)2]+ complex. (Ammine-metal complexes are numerous and have a great analytical importance—see Table 35.1. They are also of historical interest.)... 

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 ... 

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. 

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. 

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. 

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) ... 

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). 

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). 

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. 

Similarity with cobalt is also apparent in the affinity of Rh and iH for ammonia and amines. The kinetic inertness of the ammines of Rh has led to the use of several of them in studies of the trans effect (p. 1163) in octahedral complexes, while the ammines of Ir are so stable as to withstand boiling in aqueous alkali. Stable complexes such as [M(C204)3], [M(acac)3] and [M(CN)5] are formed by all three metals. Force constants obtained from the infrared spectra of the hexacyano complexes indicate that the M--C bond strength increases in the order Co < Rh < [r. Like cobalt, rhodium too forms bridged superoxides such as the blue, paramagnetic, fCl(py)4Rh-02-Rh(py)4Cll produced by aerial oxidation of aqueous ethanolic solutions of RhCL and pyridine.In fact it seems likely that many of the species produced by oxidation of aqueous solutions of Rh and presumed to contain the metal in higher oxidation states, are actually superoxides of Rh . ... 

A wide variety of complexes are formed by both metals in the +2 oxidation state indeed, it is the most important one for palladium. The complexes can be cationic, neutral or anionic. Both Pd2+ and Pt2+ are soft acids so that many stable complexes are formed with S or P as donor atoms but few with O-donors, though there are important ammines. There are pronounced similarities between corresponding palladium and platinum complexes the latter are more studied (and less labile). 

The metal-metal interaction and conductivity increase with pressure using bulkier ammines increases the Pt-Pt distance. Although palladium-containing ions can be substituted for the platinum species, the optical properties and metal-metal interaction causing pronounced dichroism are... 

Decomposition of the metal ammines have probably been most extensively investigated. Some qualitative features of the thermal decomposition of metal ammine compounds are conveniently illustrated [1116— 1118] by the somewhat contrasting behaviour of the compounds [Cr(NH3)6]X3 and [Co(NH3)6]X3 where X is Cl- or Br . During decomposition of the chromium compound, the oxidation number of the metal remains unchanged, viz. 

W.W. Wendlandt and J.P. Smith, Thermal Properties of Transition Metal Ammine Complexes, Elsevier, Amsterdam, 1967. 

One-dimensional complexes, 6,134 One-dimensional conductors, 6,134 One-dimensional metals Krogmann salts, 6, 136 Optical isomerism cobalt ammines, 1,12 history, 1,180... 

Kolis et al. reported the synthesis of some metal sulfide salts of homolep-tic lanthanide ammine complexes using supercritical ammonia as a reaction medium (Scheme 12) [49]. They proposed that these reactions proceed via a... 

Because ammine ligands are neutral molecules, the oxidation state of each metal is the same as the charge on the complex. Iron loses two of its eight valence electrons to reach the +2 oxidation state, leaving six electrons for the d orbitals. Likewise, cobalt in its +3 oxidation state has six d electrons. 

In a dissociative process the reaction rate is expected to decrease as the strength of the metal to leaving ligand bond increases. This trend is generally observed in Co(III) ammine complexes. As can be seen in Table 2, a partial leaving group order is... 

Bjerrum, J. Metal Ammine Formation in Aqueous Solution. Copenhagen P. Haase and Son 1941. 

Fig. 7.63 Mossbauer spectra of some hexacoordinated ammine and pyridine complexes of trivalent iridium taken at 4.2 K with a source of Os in Os metal. The stick spectra indicate the positions and relative intensities of the individual resonance lines (from [285])...

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