Ligand exchange mechanisms

Interaction with plurivalent cations via ligand exchange mechanism is one more rather widely applied crosslinking technique. The network bonds of ionic or donor-acceptor nature are located, with respect to lifetime, between the truly covalent crosslinks and physical entanglements. Generally speaking, gelation in these systems is reversible. 

The most widely used approach for the separation of enantiomers by TLC is based on a ligand exchange mechanism using commercially available reversed-phase plates impregnated with a solution of copper acetate and (2S,4R,2 RS)-4-hydroxy-l-(2-hydroxydodecyl)proline in optimized amounts. Figure 7.9 (10,97,98,107-109). Enantiomers are separated based on the differences in the stability of the diastereomeric complexes formed between the sample, copper, and the proline selector. As a consequence, a prime requirement for separation is that the seumple must be able to form complexes with copper. Such compounds include... 

Transmetalation, though, requires enhanced electrophilicity of the Pd. Additionally a free coordination site may be required, which may be freed by dissociation of either a neutral or an anionic ligand. The involvement of five-coordinate species and association-dissociation ligand-exchange mechanisms in the individual steps of Pd-catalyzed reactions also cannot be neglected (Scheme 3).384... 

Rates of ligand exchange depend quite strongly on the coordina-tive environment of the metal center. The water exchange rate of Fe(H2O)5(OH)is almost three orders of magnitude higher than that of Fe(H20)g+, and follows a dissociative, rather than an associative exchange mechanism (20). Fe(1120)5(OH)has also been shown to form inner-sphere complexes with phenols (27), catechols (28), and a-hydroxycarboxylic acids (29) much more quickly than Fe(H20) +. The mechanism for complex formation with phenolate anion (A-) is shown below (27) ... 

If the flexion barriers of monocentric skeletons are such that the exchange of ligands occurs only by certain mechanisms, the number of... 

Once we open the system to allow exchange of ligands between the sites and the reservoir, the number of occupancy states of our system is not Q) (or 6 in the case of Fig. 1.1), but 2 " (or 2 = 16 as in Fig. 1.2). This is so because any site can be either empty or occupied, i.e., 2 states for each site, hence 2 " states for the m sites. Clearly, in an open system these 2 " configurations are not equally probable. For calculating the probabilities of the various events statistical mechanics provides a general recipe which differs from the classical method used above. The latter is applicable only when there are Q equally probable events (say, six outcomes of casting a die with probability 1/6 for each outcome). 

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