Complex formation, kinetic consequences

Formation kinetics for eight tetraaza macrocycles of the cyclam type reacting with copper(II) have been analyzed in terms of rate constants for reaction with [Cu(OH)3] and with [Cu(OH)4]2. There is a detailed discussion of mechanism and of specific steric effects (292). Complex formation from cyclam derivatives containing -NH2 groups on the ring -CH2CH2CH2- units proceeds by formation followed by kinetically-distinct isomerization. The dramatic reactivity decreases consequent on... 

The three rate constants for Eq. (98) correspond to the acid-catalyzed, the acid-independent and the hydrolytic paths of the dimer-monomer equilibrium, respectively, and were evaluated independently (107). The results clearly demonstrate that the complexity of the kinetic processes is due to the interplay of the hydrolytic and the complex-formation steps and is not a consequence of electron transfer reactions. In fact, the first-order decomposition of the FeS03 complex is the only redox step which contributes to the overall kinetic profiles, because subsequent reactions with the sulfite ion radical and other intermediates are considerably faster. The presence of dioxygen did not affect the kinetic traces when a large excess of the metal ion is present, confirming that either the formation of the SO5 radical (Eq. (91)) is suppressed by reaction (101), or the reactions of Fe(II) with SO and HSO5 are preferred over those of HSO3 as was predicted by Warneck and Ziajka (86). Recently, first-order formation of iron(II) was confirmed in this system (108), which supports the first possibility cited, though the other alternative can also be feasible under certain circumstances. 

The monomer is but one of several competitors, whose interactions with the carbenium ion serves to lower the free energy of the system. The second important competitor is the anion, A . It forms the ion-pair Pn+A which has an even lower charge density than the Pn+M and is a strong dipole. For these reasons the formation of the doubly complexed species Pn+MA and Pn+A"M seems unlikely to be of kinetic importance. However, the formation of Pn+M does have some interesting electrochemical, and therefore also kinetic, consequences. 

Kinetics and mechanisms of complex formation have been reviewed, with particular attention to the inherent Fe +aq + L vs. FeOH +aq + HL proton ambiguity. Table 11 contains a selection of rate constants and activation volumes for complex formation reactions from Fe " "aq and from FeOH +aq, illustrating the mechanistic difference between 4 for the former and 4 for the latter. Further kinetic details and discussion may be obtained from earlier publications and from those on reaction with azide, with cysteine, " with octane-and nonane-2,4-diones, with 2-acetylcyclopentanone, with fulvic acid, and with acethydroxamate and with desferrioxamine. For the last two systems the various component forward and reverse reactions were studied, with values given for k and K A/7 and A5, A/7° and A5 ° AF and AF°. Activation volumes are reported and consequences of the proton ambiguity discussed in relation to the reaction with azide. For the reactions of FeOH " aq with the salicylate and oxalate complexes d5-[Co(en)2(NH3)(sal)] ", [Co(tetraen)(sal)] " (tetraen = tetraethylenepentamine), and [Co(NH3)5(C204H)] both formation and dissociation are retarded in anionic micelles. 

The most important reaction of this type is the formation of imine bonds and Schiff bases. For example, salicylaldehyde and a variety of primary amines undergo reaction to yield the related imines, which can be used as ligands in the formation of metal complexes. However, it is often more desirable to prepare such metal complexes directly by reaction of the amine and the aldehyde in the presence of the metal ion, rather than preform the imine.113 As shown in Scheme 31, imine formation is a reversible process and isolation of the metal complex results from its stability, which in turn controls the equilibrium. It is possible, and quite likely, that prior coordination of the salicylaldehyde to the metal ion results in activation of the carbonyl carbon to amine nucleophilic attack. But it would be impossible for a precoordinated amine to act as a nucleophile and consequently no kinetic template effect could be involved. Numerous macrocyclic chelate systems have been prepared by means of imine bond formation (see Section 61.1.2.1). In mechanistic terms, the whole multistep process could occur without any geometrical influence on the part of the metal ion, which could merely act to stabilize the macrocycle in complex formation. On the other hand,... 

Interest continues in the effects of micellar agents on rates of inorganic reactions. Aquation of oxalato-cobalt(m) and -chromium(iii) complexes is mentioned in a review of reversed micellar systems predicted and actual rates have been compared for a variety of reactions, including the mercury(n)-catalysed aquation of [CoX(NH3)g] + cations. Micellar effects on uncatalysed aquation of cis- and of tra j -[CoCl2(en)2]+ are small (as expected) but real. Other reactions for which the kinetic consequences of micelle or polyelectrolyte addition have been d cribed include complex formation from nickel(ii), the conversion of ammonium cyanate into urea, and the hydrolysis of pyrophosphate. ... 

If the chemical system has a single unstable steady state and hence shows oscillatory behavior in the absence of starch, complex formation can stabilize the homogeneous steady state and make possible the appearance of Turing structures at parameters which would yield oscillatory kinetics in the complex-free system. Observe that in the above partial differential equation system (12) the effective ratio of diffusion coefficients is (1 -f K )c, which can be much greater than unity even if c < 1. Consequently, the presence of a species that forms an appropriate complex with the activator can allow Turing structures to form for, in principle, any ratio of the activator and inhibitor diffusion coefficients. 

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