Nickel dendrimer

Fernandes, E.G.R., Vieira, N.C.S., de Queiroz, A.A.A., Guimaraes, F.E.G. Immobilization of poly(propylene imine) dendrimer/Nickel phthalocyanine as nanostructured multilayer films to be used as gate membranes for SEGEET pH sensors. J. Phys. Chem. C 114, 6478-6483 (2010)... 

An early example of a dendritie eatalyst was reported by Knapen et al. 24), who functionalized GO (generation zero) and G1 earbosilane dendrimers with up to 12 NCN pincer-nickel(II) groups (7a). These dendrimers were applied as eatalysts in the Kharasch addition of organic halides to alkenes (Seheme 3). 

Fig. 6.27 Nickel-loaded carbosilane dendrimers 1-3 of increasing generation number (GO—C2) and a corresponding non-dendritic reference substance 4...

Contrary to expectations, the catalytic activity was found to decrease with increasing generation number. This was explained in terms of the increasing spatial demands of the nickel complex units bound in increasing numbers to the dendrimer periphery and increasingly limiting access to their active sites (see Fig. 6.28). 

The decrease in catalytic activity of the nickel-containing carbosilane dendri-mer shown in Fig. 6.28 was attributed to the formation of mixed complexes with nickel in both oxidation states II and III on the dendrimer surface, which competes with the reaction with substrate radicals occurring in Kharash reactions (Fig. 6.29). 

Van Koterfs group used a chemically inert, lipophilic carbosilane dendrimer scaffold as support material for fixation of up to 12 transition metal complex fragments. The covalently fixed fragments with nickel as catalytic site acceler-... 

Their advantage over other types of dendrimers is their straightforward synthesis and, most importantly, their chemical and thermal stabilities. Two distinct steps characterize their synthesis a) an alkenylation reaction of a chlorosilane compound with an alkenyl Grignard reagent, and b) a Pt-cata-lyzed hydrosilylation reaction of a peripheral alkenyl moiety with an appropriate hydrosilane species. Scheme 2 shows the synthesis of catalysts Go-1 and Gi-1 via this methodology. In this case, the carbosilane synthesis was followed by the introduction of diamino-bromo-aryl groupings as the precursor for the arylnickel catalysts at the dendrimer periphery. The nickel centers of the so-called NCN-pincer nickel complexes were introduced by multiple oxidative addition reactions with Ni(PPh3)4. 

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]. 

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). 

For some of them, the use of membrane reactors for their recovery or application in continuously operated reactors has been demonstrated. Examples include the use of dendrimer-bound nickel catalysts for the Kharasch addition [54, 59] and dendritic palladium catalysts for an allylic substitution [73, 60]. The membrane reactor concept has also been transferred to reactions at higher pressure, as shown for the hydrovinylation of styrene (cf. Section 3.3.3) [75]. Modem ultra-and nanofiltration membranes allow an effective recovery of the homogeneously soluble catalyst. However, in some cases the long-term stability of the catalyst under operating conditions has to be improved. 

In another study also, electrochemical impedance technique has been shown to be a useful method for a DNA biosensor using a multinuclear nickel(II) salicylaldimine metallodendrimer platform [164], Both the preparation of the dendrimer-modified GCE surface and the immobilization of DNA have been effectively done by simple drop-coating procedures. The metallodendrimer is electroactive exhibiting two redox couples in phosphate buffer solution. The impedance study demonstrated that the DNA biosensor responded well to 5 nM of target DNA by displaying a decrease in charge transfer resistance in phosphate buffer solution and increase in charge transfer resistance in the presence of the [Fe(CN)6]3/4" redox probe. 

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. 

Lattermann et al. reported the first metallomesogenic dendrimer when they described results on trigonal bipyramidal metal complexes of ethylene-imine dendrimers of the first and second generation, based on derivatives of tris(2-aminoethyl)amine. Complexes of cobalt, nickel, copper, and zinc were prepared and found to exhibit relatively low temperature mesophases, which generally possessed hexagonal columnar structures. These materials therefore provided the first examples of metallomesogenic dendrimers [72,73]. 

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... 

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