Cobalt trivalent, complexes

In isolation the electron distribution in the trivalent chromium (III) ion consists of three unpaired electrons in the d shell, as indicated in line (a) of Table 5.1. In line (b) the six electron pairs donated to the central chromium atom by oxygen atoms of water molecules give rise to sp3d2 hybridisation. This is characteristic of an octahedral structure. A similar situation arises with the trivalent cobalt(III) complex in line (e), where each of the three t2g levels is doubly occupied by an electron pair from each cyano ligand. 

Despite the above similarities, many differences between the members of this triad are also to be noted. Reduction of a trivalent compound, which yields a divalent compound in the case of cobalt, rarely does so for the heavier elements where the metal, univalent compounds, or hydrido complexes are the more usual products. Rhodium forms the quite stable, yellow [Rh(H20)6] " ion when hydrous Rh203 is dissolved in mineral acid, and it occurs in the solid state in salts such as the perchlorate, sulfate and alums. [Ir(H20)6] + is less readily obtained but has been shown to occur in solutions of in cone HCIO4. 

When tt o d eigenfunctions are available, as in trivalent cobalt, quadrivalent palladium and platinum, etc., six equivalent bond eigenfunctions of strength 2.923 and directed toward the comers of a regular octahedron can be formed. These form the bonds in a great many octahedral complexes. 

It is interesting to note, as pointed out to me by Mr. J. L. Hoard, that these considerations lead to an explanation of the stability of trivalent cobalt in electron-pair bond complexes as compared to ionic compounds. The formation of complexes does not change the equilibrium between bivalent and trivalent iron very much, as is seen from the electrode potentials, while a great change is produced in the equilibrium between bivalent and trivalent cobalt. 

This small class of blue copper-complex dyes has made a significant contribution to the acid and reactive ranges in recent years (sections 5.4.2, 5.4-3 and 7.5.8). The essential chromogen is the bicyclic 1 1 chelated grouping illustrated (1.20). Trivalent metals such as chromium, nickel or cobalt will give tetracyclic 1 2 complexes with a central metal atom, analogous to conventional 1 2 metal-complex azo dyes. 

Symmetrical premetallised 1 2 metal-dye complexes of unsulphonated monoazo structures with aluminium (5.57) or trivalent iron (5.58) have been patented recently for use as solvent dyes [36]. They contain a polar methoxypropylaminosulphone grouping in each diazo component and are marketed as alkylamine salts. It remains to be seen, however, whether a full colour gamut of bright aluminium and iron complex dyes can be discovered with light fastness performance equivalent to that of currently available chromium and cobalt complex dyes. 

As we have seen earlier that the trivalent metal complexes are normally bound still more firmly due to the formation of four rings (unlike three rings with divalent metal complexes) and stable in strongly acidic solutions, for instance cobalt (Co2+) EDTA complex is fairly stable in concentrated hydrochloric acid ( 11.5 N). 

Cobalt in its trivalent state forms many stable complexes in solution. In these complexes, the coordination number of Co + is six. The Co2+ ion also forms complexes where the coordination number is four. Several complexes of both the trivalent and divalent ions with ammonia, amines, ethylene diamine, cyanide, halogens and sulfur ligands are known (see also Cobalt Complexes). 

Cobalt forms many complexes in both the divalent and trivalent states. While the d Co2+ ion exhibits a coordination number of four or six in the trivalent state, the d Co3 ion mostly exhibits coordination number six. Also, trivalent cobalt forms more stable complexes than Co2+ ion, and there are many more of them. The most common donor atom in cobalt complexes is nitrogen. 

The valency of the complex radicle is the same as that of the central metallic atom when the complex contains only ammonia, substituted ammonia, water, or other neutral group. For example, cobalt in eobaltie. salts is trivalent, and the cobalt complex with ammonia, Co(NI13)8 ", is likewise trivalent copper in cupric sulphate is divalent, and the copper complex, [Cu(NH3)4] , is also divalent. In the same wn.y [Co(NH3)5.H30] " and [Co(NII3)4.(II20)2] " are trivalent, as also [Co(NH3)2.en2]" and [Co.en3] ", where en represents cthyleucdiamine, CH NH2... 

In some instances the metal complex may become the anode instead of the cathode. The acidic radicles have, in this case, increased at the expense of ammonia until there is a greater number of acidic radicles in the complex than corresponds to the valency of the metallic atom thus [Co(NH8)s.(NO,)J. If valency is determined by the above method it is found, since cobalt is trivalent, and (N02)4 has a total valency of four, that the valency of the complex, namely, three minus four, has a unit negative value. The complex is thus anodic and unites with one atom of a monovalent metal or its equivalent. The complex radicle cited, therefore, united with potassium yields the substance [Co(NH.))2.(N02)4]K, or potassium tctranitrito-diammino-eobalt,. 

Nickel, although closely resembling cobalt, shows much less tendency to form complex radicles, and there is no long series of stable ammino-nickel salts as in the case of cobalt. Further, the stable series of ammino-derivatives of cobalt are those in which the metal is trivalent, whereas in the case of nickel the niekelie salts are unknown, and the complex ammino-derivatives are additive compounds of nickelous salts. 

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. 

Ammino-derivatives op Cobalt Salts—Cobaltous Salt Ammines—Cobaltic Salt Ammines—Mononuclear Cobalt-ammines containing One Atom of Cobalt in the Molecule—Cobaltic Salts with Trivalent Cation—Cobalt-ammines Containing Divalent Cation—Cobalt-ammines containing Monovalent Cation—Cobalt-ammines consisting of Non-dissociable Complex— Cobalt-ammines containing Monovalent Anion—Cobalt Salts containing Trivalent Anion—Polynuclear Cobalt-ammines containing Two or more Cobalt Atoms in the Molecule—Cobalt-ammines of Unknown Constitution— Ionisation Metamerism—Polymerisation Isomerism—Valency Isomerism —Co-ordination Position Isomerism—Isomerism due to Asymmetric Cobalt Atoms. 

There are ammoniates of PtCl2, of halides of other platinum metals and of cobalt and nickel, too, some of which have been mentioned before in, Section 50. The cobalt complexes clearly show the importance of the completed d shells for the stability of the complex. Non complex compounds of trivalent cobalt are very unstable. Solutions of divalent cobalt in ammonia, however, are readily oxidized by air, because the NH3 complex of trivalent cobalt Co(NH3)6 3+ClT has eighteen electrons used in bond formation, whereas the ion Co(NH3) + would have nineteen electrons. 

With its 3d84,r2 electron configuration, nickel forms Ni2 ions. Having a nearly complete 3d subshell, nickel does not yield a 3d electron as readily as iron and cobalt, and trivalent and tetravalent forms are known only in the hydrated oxides. Ni203 and Ni()2. and a few complexes. 

The classical dc polarography of vitamins A, B, B2, B6, BI2, and C, nicotinamide, tocopherols, and naphthoquinones has been reviewed [55]. Other studies have examined in detail the cyclic voltammetry of vitamin B12 employing rapid-scan voltammetry at the DME [90] and the HMDE [91]. Vitamin B12 is complexed with trivalent cobalt ion at the heterocyclic nitrogen atoms. As a result of the complexation, a catalytic hydrogen wave is formed for the compound. In addition to the catalytic wave, a wave corresponding to the reduction of the trivalent cobalt to the monovalent state is observed. 

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