Chromium ammines

Hydrolysis of ammonia or amines is often observed, but only in a few cases have such reactions proved to be useful synthetically. Base hydrolysis (aqueous NH3) of the so-called rhodo ion, (NH3)5Cr(OH)-Cr(NH3)55 +, yields the so-called cis hydroxo erythro ion, cis-(NH3)5-Cr(OH)Cr(NH3)4(OH)4+, and both this ion and its corresponding acid form, cis aqua erythro have been isolated as salts (227, 252, 253). The hydrolysis is complete within minutes, and unlike the hydrolysis of many other ammine chromium(III) complexes, is quite a clean reaction, at least in solutions of moderate alkalinity (225). The corresponding trans aqua isomer has been prepared by heating the solid... 

Gould and co-workers have reported acid dependence of the rates of reduction of acetato- and propionato-penta-amminecobalt(m) by chromium(n), vanadium(n), and europium(ii). In all cases they note a decrease in rate with increasing acidity, which in the case of the acetatopenta-ammine + chromium(n) system confirms earlier work. Assuming the protonation equilibria (22 R=Me or Et) they have fitted... 

The chromium(ii) reductions of oxalatotetra-ammine- and maleatopenta-ammine-chromium(m) have been investigated, the rate law for the oxalato-complex having the form... 

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. 

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. 

Thermally, ammine complexes of chromium(III) containing a coordinated ligand X (where X is CL, CNS , etc.) undergo substitution of X by H20 in aqueous solution with retention of stereochemistry ... 

Much less is known about photoinitiated ligand exchange reactions of coordination complexes of cobalt(III) and other de ions than is the case for chromium(III). With the exception of the cobalt(III) ammines, however, available data suggest that photochemical ligand exchange reactions of cobalt(III) and d6 systems involve the thermally equilibrated 17 g and/or 37, states of the complex as intermediates. The reasoning is completely analogous to that described earlier with respect to chromium(III) photochemistry. 

After the resolution of 1-2-chloro-ammino-diethylenediamino-cobaltie chloride many analogous resolutions of optically active compounds of octahedral symmetry were carried out, and active isomers of substances containing central cobalt, chromium, platinum, rhodium, iron atoms are known. The asymmetry is not confined to ammines alone, but is found in salts of complex type for example, potassium tri-oxalato-chromium, [Cr(Ca04)3]K3, exists in two optically active forms. These forms were separated by Werner2 by means of the base strychnine. More than forty series of compounds possessing octahedral symmetry have been proved to exist in optically active forms, so that the spatial configuration for co-ordination number six is firmly established. 

Chromium in the trivalent state forms a variety of salts, the most important and the simplest being the violet salts, which liberate in aqueous solution chromium cation Cr" A green series of chromic salts, isomeric with the violet salts, liberate in aqueous solution some chromium cation, whilst part of the chromium is present as a complex ion. With weak acids, sulphurous, hydrocyanic, or thiocyanic acids, the chromic ion forms complex ions of great stability. Finally, a very large group of salts exists where chromium associated with ammonia forms the complex ion, the chromi-ammines. 

The chromi-ammines containing one atom of chromium in the molecule form by far the largest class of these additive compounds. 

A. Mononuclear Chromi-ammines containing One Atom of Chromium in the Molecule. 

The chromi-ammines show - very clearly the parallelism between hydrated salts and ammino-salts. It has been proved that water may be gradually substituted for ammonia in the metal-ammines, and in the hexammino-salts of chromium all degrees of substitution, with, the... 

These hydroxo-salts are all sulphur-yellow crystalline substances. The acid residues are hydrolysable and hence outside the co-ordination complex, and the aqueous solutions, unlike the hydroxo-salts of chromium-and cobalt-ammines, are neutral to litmus, a fact which Werner suggests is due to the smaller tendency of the hydroxo-radicle attached to ruthenium to combine with hydrogen ions. This tendency is much less than in the case of the ammines of cobalt and chromium, but that it still exists is indicated by the increased solubility of these hydroxo-compounds in water acidified with mineral acids, and from such solutions aquo-nitroso-tetrammino-ruthenium salts are obtained thus ... 

All three elements form complex ammino-derivatives. Those of osmium have been very little investigated those of iridium are analogous to the anunino-derivatives of platinum on the one hand and to the ammincs of cobalt and chromium on the other whilst the platinum derivatives resemble those of cobalt, save that the metal in the platinic derivatives is tetravalent and not trivalent as in the cobalt-ammines. 

Ammonia unites readily with iridium salts, giving rise to complex ammino-derivatives. The first compounds described appear to be ammines analogous to those of palladium and platinum, to which they were compared by Berzelius 8 and Skoblikoff.4 A further series were described by Claus 5 wliich he represented like those of ammino-rhodium salts, as they bore a marked resemblance to these. After Jorgensen had established the constitution of the ammines of rhodium, cobalt, and chromium salts, Palmaer gave similar constitution to the iridium compounds. 

Platinum forms both platinous and platinie salts, in which the metal is divalent and tetravalent respectively. Both series of salts are capable of uniting with ammonia, forming complex ammines. The co-ordination number in the platinous series is four and in the platinie series six. The latter series correspond in many respects to the chromic and cobaltic ammino-salts, but as the metal is tetravalent, the maximum number of radicles outside the complex is four instead of three. Also, the ammino-bases from which the salts are derived are much more stable than those of chromium or cobalt. 

The electrical conductivity.—E. Klein10 showed that if there is a difference between the conductivity of a mixture of salts in soln. and the mean conductivities of the separate constituents, a double salt is probably formed. The molecular conductivity of a salt, and if possible of its components at different dilutions, has been employed to determine the number of component ions in a soln. it was used, for example, by A. Werner (1893-1901) with the cobalt, chromium, platinum, and other ammines.11 In moderately cone. soln. the double salts are but little ionized, and the difference between the conductivities of eq. soln. of potassium zinc chloride, ZnCl2.2KCl, and of the sum of the constituents amounts to nearly 36 per cent., a value which is greatly in excess of that whieh would be due to the mutual influence of salts with a common ion. Tables of the molecular conductivities of salts show that with very few exceptions, at a dilution of 1024 litres and 25°, most salts have conductivities approximating those indicated in Table XIX. 

These have been known for many years.1052-1054 Chromium(III) is approximately octahedral ( ie(f = 3.69-4.1 BM) the compounds have a layer structure. In the chloride, r(Cr—Cl) is 5.76 A between layers and 3.46 A within layers. The iodide is isomorphous with the chloride and the bromide has a similar but distinct structure. All may be prepared by the direct halogenation of the metal. Other methods are available, e.g. CrCl3 may be prepared by heating Cr203-xH20 in CCU vapour at 650 °C.1055 The anhydrous halides are insoluble in water, however reducing agents such as zinc catalyze dissolution. The trichloride reacts with liquid ammonia to form ammine complexes. 

Chromium compds, listing 3 C300—C302 chromium acetylacetone 1 A53 3 C300 chromium acetylide 1 A72 chromium (III) ammine complexes 1 A277 3C300... 

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