Acido complexes

While the liquid-liquid extraction of inorganic elements as coordination complexes with thiocyanate ions can be traced back to Skey (1867), the extraction from hydrochloric acid into ether of iron(III) (J. W. Rothe, 1892) or gallium (E. H. Swift, 1924) depends on the formation of solvated acido complexes derived from HMC14 extractions of metal complexes from nitric, thio-cyanic, hydrofluoric, hydrochloric and hydrobromic acids were studied exhaustively by Bock and his collaborators (1942—1956).6... 

The acido complexes [IrtNH jXp (X = I, Br, CHOCT, CH3COO-, N03-) for which the corresponding acids are easily available can be prepared according to the procedure given for the aquo compound. Instead of using HC104, the aquo salts are precipitated by the respective acid. The corresponding... 

This suggests either that there is no competition from acid-compound formation with the extractant or that an acido complex of the metal is extracted as in Eq. (2) (20,33) ... 

When acido groups, halides, thiocyanate, azide, acetate, and nitrate are present in the coordination sphere of cobalt(III), they appear to be oxidized in preference to coordinated ammonia. Many of the radicals thus produced are capable of oxidizing ammonia released from the complex or of interfering in other ways with the reduction process, and these systems have proved very difficult to understand even in general terms. Quantum yield and other data for a number of acidopentammine and certain other complexes are given in Table IV the data on the aquation reactions of some of the complexes are considered in Section I1I-D. 

Hydrate Isomerism.—As its name implies, this depends on the position of water in the molecule, just as in the case of the acido compounds. If two or more molecules of water are present in a molecule of ammine, the water may be present within the co-ordination complex or outside of it. For instance, the compound Cr en2.(H20)2.Br3 exists in isomeric forms. It may have all the water within the complex, in which case the formula will be [Cr en2(H20)2]Br3. In solution the whole of the bromine is precipitated by silver nitrate. On the other hand, the compound may have one molecule of water in the complex and the other outside, in which case the formula is [Cr en2(IT20)Br]Br2.H20, and only two-thirds of the bromine are precipitated by silver nitrate. Another example of this kind occurs in the cobalt series chloro-aquo-tetrammino-cobaltic chloride, [Co(NTI3)4Cl.H20]Cl2, is violet in colour, and is isomeric with dichloro-tetrammino-cobaltie chloride monohydrate, [Co(N1I3)4CI2]C1.H20, which is green. 

The name roseo-cobaltic salts was given to the series by Fremy, but it is due to the research of later investigators, notably Jorgensen, that the roseo-salts were shown to be derived from the hexammino-compounds by replacement of ammonia by water. The salts are clearly marked off from those of the acido-pentammino-series, the purpureo-salts, where acid radicle replaces ammonia in the complex ion. The valency of the complex in the aquo-pentammino-salts is not changed by the entrance of water in place of ammonia. 

Erdmann,1 in 1866, prepared the first member of this series, namely, ammonium tetranitrito-diammino-cobaltate, [Co(NH3)2(N02)4] NH4. The salt is sometimes referred to as Erdmann s salt on that account. Later, Gibbs prepared other salts of the same type, and showed that in these salts the cobalt atom, united with ammonia and acidic radicles, forms a negative radicle.2 Werner then showed that these salts form the connecting link between the neutral un-ionised complex triacido-triammino-eobalt compounds and the double salt, such as potassium eobalti-nitrite. Thus, by replacement of ammonia molecules by acid radicles a transition takes place from trinitrito-triammino - cobalt to potassium tetranitrito - diammino - cobaltate, [Co(NH3)2(N02)4]K, then to potassium pentamtrito-ammino-eobalfate. [Co(NH3)(N02)5]K, and finally to hexanitrito-cobaltate, [Co(N02)e]Iv3. Tetra-acido-diammino-cobaltates are therefore the salts of the acid tetra-acido-diammino-cobaltic acid, [Co(NH3)2R4]H. 

A major compilation of solvolytic data for octahedral complexes up to 1976 can be found in the review by Edwards et a/.126 and an extensive review by House127 covers the acido—pentaamine complexes of Co(III) and Cr(III). Both are limited to substitutionally inert complexes and this section of the chapter will also be so restricted in order to allow an independent examination of the variables, in so far as they can be conveniently separated. 

One of the first differences to be noted about the Rhm acido-amine complexes is that the chloro complexes are frequently much more stable with respect to solvolysis than their Co111 and Cr111 analogues and solvolytic equilibrium is reached when very little of the chloro complex has aquated, even in dilute solution and in the absence of added chloride ions. This is, to some extent, the consequence of the move away from class a character already mentioned above. As a result, the rate constants for aquation are obtained from ligand substitution reactions (including chloride exchange) which first have to be shown to be mediated by a rate determining aquation. More recently, data have been obtained from a study of the solvolysis in basic solution. This serves to... 

Certain octahedral complexes, particularly the acido—amine complexes of cobalt(III), undergo substitution in protonic solvents at rates that are proportional to the concentration of the conjugate base of the solvent (e.g. OH- in water) or inversely proportional to the concentration of the conjugate acid of the solvent (e.g. retardation by H30+ in water or NH4+ in liquid ammonia). Such reactions have received considerable attention since systematic studies of ligand substitution commenced, and figured amongst the earliest kinetic studies in the field.298 The subject has been... 

The first coordination sphere of acido-pentamine [Cr(NH3)5X]2+ complexes has C4v symmetry and this leads to a tetragonal resolution of the 2Eg state into 2At and 1Bl components. The classical ligand field model predicts that these components will be virtually degenerate. This is based on a combination of pseudo-spherical and quasi-spin selection rules of the shell and will be discussed later on in Sect. 5.2. At present we welcome this example of a pseudo-degeneracy as another opportunity to observe fine details of the interelectronic repulsion interaction which have the proper anisotropy to induce a splitting of the 2Eg term. 

LMCTegrc0 tj(x is placed at a higher energy than the lowest lying acido ligand to Co (III) excited states and photoredox reactions are, respectively, initiated in each of these excited states, a nonradiative conversion of one into the other electronic state must be sluggish or not available. The experimental observations clearly demonstrate that the photophysics of LMCT states in complexes Com(NH2R)sX2 + with R = alky is different from that with R = H and exemplifies how the properties of the excited state have control over the photochemical properties. 

Mixed acido-molecular metal complexes, for example, [Cr(H20)5Cl] Cl2 2H20. 

Many methods have been used for the preparation of various acidopentammineeobalt(III) salts.1 In some instances these procedures are specific for the synthesis of a particular salt. The procedure suggested here involves the reaction of carbonatopentamminecobalt(III) nitrate with an acid or acid salt. The resulting reaction mixture may then be digested for a short time to yield the desired product, or the aquo complex is isolated and converted to the acido compound at an elevated temperature. This method appears to be completely general and has been used to synthesize complexes containing coordinated bromide, chloride, thiocyanate, sulfate, formate, and various substituted acetates, benzoates, and benzenesulfonates in addition to those described here. 

The ammonia and amine complexes are the most numerous chromium derivatives and the most extensively studied. They include the pure ammine [CrAm6]3+, the mixed ammine-aqua types, that is, [CrAm4 (H20) ]3+ (n = 0-4, 6), the mixed ammine-acido types, that is, [CrAm6 X ](3" )+ (n = 1-4, 6), and mixed ammine-aqua-acido types, for example, [CrAm6 m(H20) Xm](3 m7+ (here Am represents the monodentate ligand NH3 or half of a polydentate amine such as ethylenediamine, and X an acido ligand such as halide, nitrite, or sulfate ion). These complexes provide examples of virtually all kinds of isomerism possible in octahedral complexes. 

TABLE 3 Reaction yields of amine and acido ligand aquation in aqueous solutions of Cr(III) complexes at ambient temperatures... 

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