Peripheral-Functionalized Catalysts

Based on these preliminary results, a small library of NCN-pincer nickel-containing metallodendrimers was prepared by Van Koten et al. in order to investigate the factors that can affect the catalyst performance and their applicability in nanofiltration membrane reactors [35,36]. The strategy in this 

Although these synthetic routes are effective, some problems were observed in the last reaction step. Spectroscopic and elemental analysis indicated that the nickellation of the pincer moiety was incomplete, giving an average of 80 to 90% of metallated pincer sites per dendrimer. This observation was rationalized by partial hydrolysis of the reactive lithiated species prior to the introduction of the nickel reagent, causing incomplete metalla-tion of the ultimate dendrimer species [37,38]. 

This result, caused by the proximity effect between peripheral catalytic sites, can translate into higher or lower catalytic activity of the metallodendrimer in homogeneous catalysis, and is commonly termed the dendritic effect. In the above case, a negative dendritic effect is observed. An interesting example of a positive dendritic effect on catalyst activity was reported by Jacobsen et al. in the hydrolytic kinetic resolution of terminal epoxides by peripherally Co(salen)-substituted PAMAM dendrimers [39]. 

The pincer-based carbosilane dendrimers Go-2 and Gi-2 were tested for their degree of retention in a membrane reactor equipped with a SelRO-MPF-50 nanofiltration membrane [35,36]. Their retentions were measured 

The synthesis of dendritic carbosilanes functionalized with various diphenylphosphino carboxylic acid ester endgroups has also been reported by the Van Koten group in collaboration with Vogt et al. [40,41], The coupling of carbosilane supports containing benzylic alcohol moieties with phos-phinoxy carboxylic acid chlorides resulted in the formation of Go and Gi phosphine oxides, which subsequently were converted into the phosphino 

---

The applicability of this type of dendritic catalyst in a CFMR was tested for G2-I7. It was observed that the catalytic activity remained almost constant for up to eight hours of reaction time, which is in contrast with the peripheral-functionalized catalysts (Gi-7, Scheme 7) applied under similar conditions. Although resulting in an overall lower activity per catalytic center, the location of the catalytic site within the dendritic sphere seems to protect the active species against deactivation via interaction with the membrane or with other metallodendritic species. 

Dendrimers are not only unreactive support molecules for homogeneous catalysts, as discussed in the previous paragraph, but they can also have an important influence on the performance of a catalyst. The dendrons of a dendrimer can form a microenvironment in which catalysis shows different results compared to classical homogeneous catalysis while peripheral functionalized dendrimers can enforce cooperative interactions between catalytic sites because of their relative proximity. These effects are called dendritic effects . Dendritic effects can alter the stability, activity and (enantio)selectivity of the catalyst. In this paragraph, different dendritic effects will be discussed. 

Kenawy 64) immobilized ammonium and phosphonium peripheral functionalized dendritic branches on a montmorillonite supported chloromethylstyrene/methyl methacrylate copolymer (74-75). These polymer/montmorillonite-supported dendrimers were used as phase transfer catalysts (PTC) for the nucleophilic substitution reaction between -butyl bromide and thiocyanate, cyanide, and nitrite anions in a toluene or a benzene/water system. These PT catalysts could be recycled by filtration of the functionalized montmorillonite from the reaction mixture. Generally,... 

Solid-Supported Peripherally Functionalized Chiral Dendrimer Catalysts... 

Similar applications of chiral titanium Lewis acid catalysts to asymmetric [2 + 2] cycloadditions, with up to nearly quantitative asymmetric induction, have employed 4-benzoquinones as additions and substituted styrene-type substrates11. In all of these asymmetric [2 + 2]-cvcload-dition reactions, the Lewis acid catalyst presumably is attached to peripheral functional groups and thus, similar to Lewis acid catalyzed Diels Alder reactions (see Section 1.5.8.3.5.4.), is only indirectly involved in the reaction course7. 

Heptamethylcob3rrinate cobester (13) and peripherically functionalized derivatives of 13 were used as catalysts to mimic the rearrangement catalyzed by the coenzyme Bi2-dependent enzyme methylmalonyl-CoA mutase (see Fig. 13) (45). In these studies, the reductive transformation of bromomethyl-malonates to succinates, catalyzed by 13, and similar rearrangement reactions were observed (45). 

Well-defined complicated macromolecular structures require complex synthetic procedures/techniques and characterization methods. Recently, several approaches leading to hyperbranched structures have been developed and will be the focus of this section. The preparation of hyperbranched poly(siloxysilane) has been reported [198] and is based on methylvinyl-bis(dimethyl siloxysilane), an A2B type monomer, and a progressive hydrosi-lylation reaction with platinum catalysts. An appropriate hydrosilylation reaction on the peripheral - SiH groups led to the introduction of polymeric chain (PIB, PEO) or functional groups (epoxy, - NH2) [199]. 

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. 

The resulting peripheral phosphine-functionalized dendrimers were used as a ligand in the palladium-catalyzed allylic amination of crotyl acetate in a CFMR. The active catalysts were prepared by mixing all three components the dendrimer, the phosphine ligand and a suitable palladium precursor [(crotyl)PdCl]2. The catalytic activity and selectivity of 16 in a batch process... 

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). 

The periphery of convergently synthesized den-drimers has also been modified to allow the assembly of monolayers,494 to support dendritic catalysts,495 to control the intermolecular assembly of porphyrin dendrimers,246 to probe the effect of photo isomerization,319 and to enable cross-linking of the periphery followed by removal of the core.496 These studies in peripheral modification highlight the versatility of the convergent synthesis. In particular, the ability to selectively modify the periphery and focal functionalities of a dendron enables the design of complex macromolecules that involve the interaction between multiple functional components. 

Figu re 4.1 Commonly encountered chiral catalyst immobilization on dendritic polymer supports (a) core-functionalized chiral dendrimers (b) peripherally modified chiral dendrimers (c) solid-supported dendritic chiral catalysts. 

In order to facilitate recycling of the multiple TsDPEN-functionalized dendrimer catalysts, the same group recently reported the synthesis of a novel form of hybrid dendrimer ligands by coupling polyether dendrons with peripherally TsDPEN-functionahzed Newkome-type poly(ether-amide) dendrimer (Figure 4.28) [90]. The solubility of these hybrid dendrimers was found to be affected by the generation of the polyether dendron. The ruthenium complexes produced were applied in the asymmetric transfer hydrogenation of ketones, enones, imines and activated... 

The small particle size of the silica is important not only in enabling the silica to flow to the peripheral region of the porous microsphere but also in forming the hard peripheral oxide-rich shell. Particles of silica 2-3 nm in diameter sinter together to some extent even under the temperature conditions encountered in a conventional spray drying process, whereas particles 10-100 nm do not sinter below 700-1000°C. As a result, attrition resistance of the catalyst, catalyst precursor or catalyst support particle is a function of the particle size and degree of aggreggation of the silica formed by dehydration. 

In conclusion, FeP/Cu and peripherally metallated CoTPyPs such as CoTCP were found to be excellent catalysts for the four-electron reduction of O2 to H2O in slightly acidic or neutral aqueous solutions. The first one was conceived as a truly biomimetic compound while the second are functional models. It is impressive how closely Collman et were able to reproduce the structure and... 

---