Ligands, directing effects

Fig. 6.10 Examples of the directional effect of oxide ligand arrangement on the location of hard cations and orientation of M-O linkages.

The coordination of ligands at the surface of metal nanoparticles has to influence the reactivity of these particles. However, only a few examples of asymmetric heterogeneous catalysis have been reported, the most popular ones using a platinum cinchonidine system [65,66]. In order to demonstrate the directing effect of asymmetric ligands, we have studied their coordination on ruthenium, palladium, and platinum nanoparticles and the influence of their presence on selected catalytic transformations. 

The directive effect of allylic hydroxy groups can be used in conjunction with chiral catalysts to achieve enantioselective cyclopropanation. The chiral ligand used is a boronate ester derived from the (VjA jA N -tetramethyl amide of tartaric acid.186 Similar results are obtained using the potassium alkoxide, again indicating the Lewis base character of the directive effect. 

A site-inversion mechanism (the key feature of which is that isomerization between diastereomeric and A configurations is rapid on the propylene-insertion time scale) based on theoretical calculations was proposed by Cavallo and coworkers in order to explain the ligand-directed chain-end controlled polymerizations (Fig. 35) [42]. The site-inversion mechanism allows chain-end control to work in concert with the site control effects. Our experimental results and the expected catalytic behavior resulting from the site-inversion mechanism concur with each other very well. 

Though the models discussed above have great mechanistic value, the catalytic properties are complicated by the presence of cofactors, such as the structure of cocatalyst and the nature of the phosphine ligands. The effect of these cofactors on the catalytic properties can be used to optimize the catalyst activity or to direct the course of the reactions. To... 

The behaviour of natural ligands has been discussed in Section 4.3.3. In addition to the direct effect of complexation that is related to a decrease in the free ion activity, it has been shown that some ligands, in particular the HS, can be sorbed directly to biological surfaces, in the presence or absence of the trace metal [228,229]. This result is likely due to the fact that HS and similar macromolecules contain hydrophobic moieties that facilitate their adsorption to the plasma membrane and cell wall [157,230,231]. Because adsorption is expected to occur primarily with sites that are independent of the transporters,... 

We will first describe a relatively simple scenario for the enhancement of the dissolution of Al203 by a (complex-forming) ligand. As we have seen ligands tend to become adsorbed specifically and to form surface complexes with the AI(III) Lewis acid centers of the hydrous oxide surface. They also usually form complexes with AI(III) in solution. Complex formation in solution increases the solubility. This has no direct effect on the dissolution rate, however, since the dissolution is surface-controlled. 

The lack of any directing effect from the 4-methoxy and the 5-ethyl substituents at the two stereocenters already present in 71 is a remarkable finding, and points to strong catalyst-dependence in the stereocontrol (Scheme 7.20). On the basis of these findings, various stereoisomers of 3,4,4,5-tetrasubstituted cyclohexanones are now accessible through sequential catalytic 1,4-additions, with control over the relative and absolute configurations possible simply by judicious selection of the appropriate enantiomer of the chiral ligand in each step. 

The porphyrin ligand is sufficiently flexible to adopt nonplanar conformations in response to steric or electronic effects induced by the central metal, the axial ligands, or substitution at the porphyrin periphery. Coordination of the small, nonmetallic Si(IV), Ge(IV), P(V), and As(V) ions to porphyrins offer an ideal opportunity to study not only the direct effect on this phenomenon of... 

The directive effect of allylic hydroxyl groups can be used in conjunction with chiral catalysts to achieve enantioselective cyclopropanation. The chiral ligand used is a boronate... 

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