Cobalt aquation

The earliest investigation of the exchange reaction between the aquated ions of Co(III) and Co(II) was carried out by Hoshowsky et al., using the isotopic method ( Co). When sulphate salts ( 10 M) were employed, complete exchange was observed between the two oxidation states of cobalt, in a time of less than two min. Two separation methods were employed (a) adsorption on an alumina column, and (b) precipitation of the Co(III) as the cobaltinitrite. 

Rate Constants for Aquation and for Base Hydrolysis of Selected penta-ammine-Cobalt(III) Complexes a... 

Kinetic parameters for aquation at corresponding Cr(III) and Co(III) complexes have been compared for a series of complexes cis-[ML4XY]"+, where L4 = (NH3)4 or (en)2, X = Cl- or H20, and Y=an uncharged leaving group (DMSO, DMF, or DMAC). The uniformly negative activation volumes (AV between —2 and —11 cm3 mol-1) for the chromium complexes contrast with uniformly positive activation volumes (A V between +3 and +12 cm3 mol-1) for the cobalt complexes - AV values provide a more clear-cut contrast than AS values here (22). 

Hydrolysis of coordinated ligands is a special case of nucleophilic attack. Two examples involving inorganic ligands have already been given in Section II. A on aquation of cobalt(III) complexes. Many further examples will be found in the following Section VII.B on catalysis of hydrolysis of organic substrates by metal ions and complexes. 

The chemical reactivity of crown-ether complexes with neutral molecules has received little attention. Nakabayashi et al. (1976) have reported crown-ether catalysis in the reaction of thiols with l-chloro-2,4-dinitrobenzene. The catalytic activity was attributed to deprotonation of thiols by dicyclohexyl-18-crown-6 in acetonitrile solution. Blackmer et al. (1978) found that the rate of aquation of the cobalt(III) complex [333] increases on addition of... 

Manganese is an important element in the aquatic environment. It is an essential micronutrient U 2) and is the subject of much interest because its oxides scavenge other heavy metals (3). Of particular interest are ferromanganese nodules, which are abundant in the aquatic environment. These nodules contain high concentrations of cobalt, nickel, copper and other heavy metals (4). 

Many aquatic organisms exhibit an ability to concentrate a variety of trace elements and this ability has been identified as a function of the tendency of the elements to be complexed by ligands (159). The alkaline earth metals are poorly com-plexed in relation to the transition metals, copper, nickel, cobalt, zinc and manganese. The actinides should be regarded as members of an intermediate group. It has been suggested by Martin (160) that at least five mechanisms may regulate the uptake of metals by marine biota. These are... 

The plot of log kf vs log X, is linear over a wide range of rate constants (Fig. 2.7). Obviously, the faster the aquation, the more the reaction goes to completion The sloped is 1.0 and this indicates that the activated complex and the products closely resemble one another, that is, that has substantially separated from the cobalt and that therefore the... 

The aquated Co(III) ion is a powerful oxidant. The value of E = 1.88 V (p = 0) is independent of Co(III) concentration over a wide range suggesting little dimer formation. It is stable for some hours in solution especially in the presence of Co(II) ions. This permits examination of its reactions. The CoOH " species is believed to be much more reactive than COjq Ref. 208. Both outer sphere and substitution-controlled inner sphere mechanisms are displayed. As water in the Co(H20) ion is replaced by NHj the lability of the coordinated water is reduced. The cobalt(III) complexes which have been so well characterized by Werner are thus the most widely chosen substrates for investigating substitution behavior. This includes proton exchange in coordinated ammines, and all types of substitution reactions (Chap. 4) as well as stereochemical change (Table 7.8). The CoNjX" entity has featured widely in substitution investigations. There are extensive data for anation reactions of... 

Half-reactions Involving Aquated Cobalt(II) and Cobalt(III). 532... 

Half-reactions Involving Aquated Cobalt(ll) and Cobalt(lll)... 

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. 

I think in the current paper, Dr. Wilmarth s paper worked on by Dr. Haim, the acid catalysis of the aquation of the azide system is an example of what I call an off-site reaction. The attachment of hydrogen to nitrogen, which is three atoms away from the cobalt atom bringing about a weakening of the cobalt nitrogen bond and—if I remember the figures correctly—a 3500-or 5800-fold increase in the rate of aquation. 

In their first publication on this subject,59 Werner and Miolati showed that the molecular conductances (fx) of coordination compounds decreased as successive molecules of ammonia were replaced by acid residues (negative groups or anions). For cobalt(III) salts, they found that fi for luteo salts (hexaammines) > fi for purpureo salts (acidopentaammines) > /t for praseo salts (di-acidotetraammines). The conductance fell almost to zero for the triacidotriammine Co(N02)3-(NH3)3 and then rose again for tetracidodiammines, in which the complex behaved as an anion. By such measurements, Werner and Miolati determined the number of ions in complexes of cobalt(III), platinum(II) and platinum(IV). They not only found support for the coordination theory, but they also elucidated the process of dissociation of salts in aqueous solution and followed the progress of aquations. 

Table 6 Rate Constants and Activation Parameters for the Aquation of rrans-Dichloro(tetraamine)cobalt(IIl) Cations,...

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