Carbosilane metallodendrimers

Ni-Based Dendritic Catalysts. One of the first reported examples of a metalloden-drimer catalyst32 resulted from the attachment of monoanionic chelating N-C-N -type pincer moieties to the periphery of a carbosilane dendrimer, followed by the complexation of nickel(II) ions.22,23,33,34 These pincer-based carbosilane metallodendrimers (Figure 10.2) have been used... 

Carbosilane metallodendrimers were purified, isolated as cesium salts, and fully characterized by FTIR, H, "B, C, and Si NMR and UV-vis spectroscopy. The silyl-containing cobaltabis-dicarbollides show absorption bands at 310 and 462 nm in the UV-vis spectra that follow the... 

SCHEME 27.14 Preparation of a carbosilane metallodendrimer decorated with eight cobaltabisdicarbollide units. 

The research group of Van Leeuwen reported the use of carbosilane de-ndrimers appended with peripherial diphenylphosphino end groups (i.e. 25, Scheme 26) [37]. After in situ complexation with allylpalladium chloride, the resultant metallodendrimer 25 was used as catalyst in the allylic alkylation of sodium diethyl malonate with allyl trifluoroacetate in a continuous flow reactor. Unlike in the batch reaction, in which a very high activity of the dendrimer catalyst and quantitative conversion of the substrate was observed, a rapid decrease in space time yield of the product was noted inside the membrane reactor. The authors concluded that this can most probably be ascribed to catalyst decomposition. The product flow (i.e. outside the membrane reactor)... 

The first example of a catalytically active metallodendrimer, having catalytic groups at the periphery, was reported by van Koten, van Leeuwen and coworkers [20]. These authors prepared the nickel(II) complexes containing carbosilane dendrimers, which were successfully employed in the homogeneous regioselective Kharasch addition of polyhalogenoalkanes to the terminal C=C double bonds. Since these early studies there has been a steadily increasing number of dendrimer catalysts which have been synthesized and studied [15]. In this section, the details of peripherally modified chiral dendrimer catalysts for different asymmetric catalytic reactions will be summarized. 

Recently, we have also reported the synthesis of carbosilane and carbosiloxane metallodendrimers that contain one, four, and eight peripheral cobaltabisdicarbollide derivatives (Scheme... 

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