Cobalt labile

The superb elegance of this demonstration lies in the choice of reactants which permits no alternative mechani.sm. Cr" (d ) and Co" (d ) species are known to be substitutionally labile whereas Cr" (d ) and Co " (low-spin d ) are substitutionally inert, Only if electron transfer is preceded by the formation of a bridged internrediate can the inert cobalt reactant be persuaded to release a Cl ligand and so allow the quantitative formation of the (then inert) chromium product. Corroboration that electron transfer does not occur by an outer-sphere mechanism followed by los.s of CP from the chromium is provided by the fact that, if Cl is added to the solution, none of it finds its way into the chromium product. 

As with rhodium (and cobalt), introduction of five ammonia molecules is relatively straightforward, but the sixth substitution is difficult, requiring more forcing conditions. One versatile route involves the formation of the pentammine triflate complex ion [Ir(NH3)5(03SCF3)]2+, where the labile triflate group is readily replaced by water, then by a range of anionic ligands [148]. 

As already mentioned, complexes of chromium(iii), cobalt(iii), rhodium(iii) and iridium(iii) are particularly inert, with substitution reactions often taking many hours or days under relatively forcing conditions. The majority of kinetic studies on the reactions of transition-metal complexes have been performed on complexes of these metal ions. This is for two reasons. Firstly, the rates of reactions are comparable to those in organic chemistry, and the techniques which have been developed for the investigation of such reactions are readily available and appropriate. The time scales of minutes to days are compatible with relatively slow spectroscopic techniques. The second reason is associated with the kinetic inertness of the products. If the products are non-labile, valuable stereochemical information about the course of the substitution reaction may be obtained. Much is known about the stereochemistry of ligand substitution reactions of cobalt(iii) complexes, from which certain inferences about the nature of the intermediates or transition states involved may be drawn. This is also the case for substitution reactions of square-planar complexes of platinum(ii), where study has led to the development of rules to predict the stereochemical course of reactions at this centre. 

On the other hand, if electron transfer does occur within this bridged complex, a bridged cobalt(ii) - chromium(iii) complex is generated (Eq. 9.36). The d cobalt(ii) center is labile whilst the d chromium(iii) center is inert. 

If this complex now collapses, it will be the labile Co-Cl bond which is broken, as opposed to the inert Cr-Cl bond. The labile cobalt(ii) complex reacts further with bulk water to generate [Co(H20)6] (Eq. 9.37). The key feature is that a necessary consequence of this inner-sphere reaction is the transfer of the bridging ligand from one center to the other. This is not a necessary consequence of all such reactions, but is a result of our choosing a pair of reactants which each change between inert and labile configurations. In the reaction described above, the chloride... 

The most extensively studied family of non-labile complexes is the cobalt(III) ammine series. These are octahedral systems and all those to be considered are low spin <7 systems. The subtle variations that can be achieved synthetically make... 

The membrane-bonnd dehalogenase from Dehalobacter restrictus contained (per mole of subunit) 1 mol of cobalamin, 0.6 mol cobalt, 7 mol iron, and 6 mol acid-labile sulfur. 

There is a large amount of data available concerning the thermodynamic effects of ligands on other coordination sites (i. e., the thermodynamic cis- and iraws-effects). However, very little is known about the effects of ligands on the kinetic lability of other coordination sites. In fact, very little work has been carried out, directly with Bi2-derivatives, or with models of B12, on the kinetics of ligand substitution at the cobalt center. Of particular biochemical interest would be studies on the rate of displacement of coordinated benzimidazole by various ligands. Such work has not been reported at present. If the benzimidazole is replaced during enzymatic catalysis so that the lower axial position is occupied by some other Lewis base, one would expect this displacement, and the reverse step, to be very facile. This appears to be qualitatively true in that when water displaces benzimidazole as the benzimidazole is pro-... 

Batley and Matousek [390,778] examined the electrodeposition of the irreversibly reduced metals cobalt, nickel, and chromium on graphite tubes for measurement by electrothermal atomisation. This method offered considerable potential for contamination-free preconcentration of heavy metals from seawater. Although only labile metal species will electrodeposit, it is likely that this fraction of the total metal could yet prove to be the most biologically important at the natural pH [779]. 

The NO/NO+ and NO/NO- self-exchange rates are quite slow (42). Therefore, the kinetics of nitric oxide electron transfer reactions are strongly affected by transition metal complexes, particularly by those that are labile and redox active which can serve to promote these reactions. Although iron is the most important metal target for nitric oxide in mammalian biology, other metal centers might also react with NO. For example, both cobalt (in the form of cobalamin) (43,44) and copper (in the form of different types of copper proteins) (45) have been identified as potential NO targets. In addition, a substantial fraction of the bacterial nitrite reductases (which catalyze reduction of NO2 to NO) are copper enzymes (46). The interactions of NO with such metal centers continue to be rich for further exploration. 

The above value of k4 1 s for bpy loss from Rh(bpy)3 + may be compared with k4 - 3 s for bpy loss from the formally related Co(bpy)32+ (13,14) Recently obtained results indicate that the rate constant for addition of bpy to Rh(bpy)2(H2O)2 (k 4 s 0.2 x lO Ms"1) is greater than that for the comparable cobalt(II) reaction (13,14) The more-or-less comparable labilities of Rh(bpy)3 T and Co(bpy)3 + are not unexpected in light of data for rates of ammonia loss from the two metal centers which are also available ammonia loss from rhodium(II) is quite rapid (10 s 1 to 10 s l with loss from Rh(NH3)5 H20 + being much faster than from Rh(NH3)4 +, etc ) W t>ut somewhat slower than the comparable process for cobalt(II) (15) Of course, here the relative affinities of the two metals for NH3 are not known and so cannot be taken into account A further reason these comparisons lack great validity is that, although these Co(II) complexes contain 3d metal centers, Co(bpy)3 + and Co(NH3)n + are high-spin complexes i.e. the ground states are (t2g) (eg) whereas 4d species are expected to be low spin, (t2g) (eg)1. Furthermore, as will be seen shortly it is not clear that even "low spin 4d " is an adequate description of 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... 

Although Co(III) is often considered the classical representative of inert behavior, there are a number of cobalt(III) complexes that react rapidly enough to require that the rates be determined by flow methods. Table 8.11 shows a representative selection of such labile complexes. 

There have been few studies of substitution in complexes of nickel(II) of stereochemistries other than octahedral. Substitution in 5-coordinated and tetrahedral complexes is discussed in Secs. 4.9 and 4.8 respectively. The enhanced lability of the nickel(II) compared with the cobalt(II) tetrahedral complex is expected from consideration of crystal field activation energies. The reverse holds with octahedral complexes (Sec. 4.8). 

However, beeause of the kinetie lability of eobalt(ll), heterogenized catalysts based on Co are suseeptible to metal leaehing during liquid phase reaetions and thus repeated use of such catalysts is not practical from a chemical point of view. In order to avoid this problem, use of catalysts based on cobalt(lll), whieh is substitutionally inert, may be expected to show more attraetive eatalytic properties for the same reaetions. As expeeted, substitutionally inert cobalt(lll) eomplexes have been shown to be eatalytieally very aetive, and henee attractive, for alkylaromatie oxidation [26]. Also, as we shall see later, a series of tetramerie eobalt(lll) complexes eapable of cycling oxidation states between 111 and IV has also been foimd to be effective as eatalysts for the oxidation of alkyl aromaties, aleohols and alkenes [5,15,27]. 

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