Functional periphery

Synthesis of Periphery-Functionalized Dendritic Molecules Using Polylithiated Dendrimers as Starting Material, P. 

The dendrimer framework also plays an important role. The catalytic performance measured by activity, selectivity, stability, and recyclability depends on the dendritic architecture, and it is important to distinguish periphery-functionalized, core-functionalized, and focal point-functionalized dendrimers (Fig. 1). Periphery-functionalized dendrimers have catalytic groups located at the surface where they are directly available to the substrate. In contrast, when a dendrimer is functionalized at its core, the substrate has to penetrate the dendrimer support before it reaches the active center, and this transport process can limit the rate of a catalytic reaction if large and congested dendrimers are involved. 

The accessible peripheral catalytic groups enable reaction rates that are comparable to those of homogeneous systems, but the periphery-functionalized dendrimers contain multiple reaction sites and may have extremely high local catalyst concentrations, which can lead to cooperative effects in reactions that proceed via a... 

Another noteworthy difference between core- and periphery-functionalized dendrimers is that much higher costs are involved in the application of core-functionalized dendrimers due to their higher molecular weight per catalytic site. Furthermore, applications may be limited by the solubility of the dendrimer. (To dissolve 1 mmol of catalyst/L, 20 g/L of core-functionalized dendrimer is required (MW 20 000 Da, 1 active site) compared to 1 g/L of periphery-functionalized dendrimer (MW 20 000 Da, 20 active sites). On the other hand, for core-functionalized systems, the solubility of the dendritic catalyst can be optimized by changing the peripheral groups. 

In periphery-functionalized dendritic catalysts, the functional groups at the surface determine the solubility and miscibility and thus the precipitation properties. Many dendrimers functionalized with organometallic complexes do not dissolve in apolar solvents, and the presence of multiple metal centers at the periphery facilitates precipitation upon addition of this type of solvent. It is emphasized that the use of dendrimer-immobilized catalysts with the goal of recovery through precipitation is worthwhile only if the tendency to precipitation of the dendritic system exceeds that of its non-dendritic equivalent. 

Maraval et al 39) synthesized core- and periphery-functionalized ruthenium and palladium dendritic diphosphines (Fig. 12) that were applied in three reactions (Stille coupling, Knoevenagel condensation, and diastereoselective Michael addition). The catalyst was recovered by using the precipitation strategy. 

The properties induced by the dendritic framework depend on the location of the functional groups within the structure. Periphery-functionalized dendrimers offer high accessibility of the metal complex, which allows reaction rates that are... 

A general trend observed in many of the reports concerning catalysis with periphery-functionalized dendrimers is that the activity of the catalysts decreases with the dendrimer generation, which is usually attributed to the increasing steric bulk around the metal centers as the dendrimer generation increases. Some of these negative effects have already been discussed in Section II. 

Percec V, Cho WD, Ungar G. Increasing the diameter of cylindrical and spherical supramolecular dendrimers by decreasing the solid angle of their monodendrons via periphery functionalization. J Am Chem Soc 2000 122 10273-10281. 

Core-functionalized metallodendrimers have the advantage of creating isolated sites due to the environment of the dendritic framework. In the case of core-functionalized dendrimers, the molecular weight per catalytic site (ligand/catalyst) is higher than for periphery-functionalized dendrimers, which therefore involves higher costs from a commercial point of view. The... 

In this system, the catalyst G3-I9 showed a similar reaction rate and turnover number as observed with the parent unsupported NCN-pincer nickel complex under the same conditions. This result is in contrast to the earlier observations for periphery-functionalized Ni-containing carbosilane dendrimers (Fig. 4), which suffer from a negative dendritic effect during catalysis due to the proximity of the peripheral catalytic sites. In G3-I9, the catalytic active center is ensconced in the core of the dendrimer, thus preventing catalyst deactivation by the previous described radical homocoupling formation (Scheme 4). 

Nonetheless, the transposition of homogeneous catalytic reactions from unsupported to dendrimer-supported catalysts is still not straightforward. Various dendritic effects , positive and negative ones, on the activity, selectivity, stability and solubility of metallodendrimer catalysts have been observed in this respect. In our own research we have found that a high concentration of metal centers at periphery-functionalized metallodendrimers may translate into a decrease in the catalytic performance due to undesirable side-reactions between the catalytic sites at the dendrimer surface (Fig. 4 and Scheme 4). In contrast, when the exact same catalyst is located at the focal point of a dendron, this matter is avoided by isolating the active site, thereby providing a more stable albeit less active catalyst (Scheme 13). 

Abstract New polymeric supports, that can be used for preparation of novel catalytic systems, were obtained by grafting poly(vinylmethyl-co-dimethyl)siloxane arms onto multifunctional carbosilane moieties which belong to the class of exceptionally sterically hindered tris(silyl)methanes (Tj,.). Three types of Tj, molecules were applied 3-functional HCCSiMe Br) (type A), 9-functional HC[SiMe2(CHj)j-C (SiMejBr) ] (type B) and 4-functional Tg -derivative [SiMe2C(SiMe2Br)j]j (type C). The periphery-functionalized carbosilane-siloxane materials offer uniformly distributed and accessible sites for coordination of active catalytic species. New catalytic systems were thus prepared by coordination of platinum to vinyl moieties of the reported polymers, and used in hydrosilylation of vinyltrimethylsilane with 1,1,3,3-tetramethyldisiloxane. 

We would like to report the synthesis of a star-shape poly(vinylmethyl-c6>-dimethyl)siloxane polymers functionalized in their exterior, which makes them especially suitable for application as catalytic supports. Similarly to catalysts bound to periphery-functionalized dendrimers [3] they offer regularly distributed and available catalytic sites. 

In contrast to the core-functionalized systems, periphery-functionalized dendrimers have their catalytically active groups located at the surface of the den-... 

Periphery-functionalized %ands and their appHcation in transition-metal-catalyzed reactions 12YGK928. 

Scheme 2.36 Synthesis of periphery-functionalized dendrimeric phosphines.

Apparently, periphery-functionalized dendrimers have the ligands and/or catalysts at the surface of the dendrimer. The transition metals will be directly exposed... 

---