Polystyrene complexes attached

Similar results were reported by Kim et al. [45 a] and Che et al., [83] who both employed salen complexes attached to zeolite MCM-41. Similarly, Seebach and coworkers generated dendritic elongated salen derivatives that could be embedded in polystyrene by co-polymerization [80]. 

Electron-transfer Reaction of the Metal Complexes Attached to Polystyrene Beads... 

The DlOP-rhodium(I) complex attached to organic polymers , e.g., polystyrene resin and poly(methyl vinyl alcohol), exhibits good catalytic activity as a chiral catalyst comparable to the corresponding homogeneous catalyst. In contrast, the rhodium(I) complexes anchored on inorganic supports display only a low efficiency . Studies show that the steric requirements for a match of the chiral ligand, a hydrosilane and a ketone are of definite importance in bringing about effective asymmetric induction. 

Rhodacarborane catalysts have been immobilized by attachment to polystyrene beads with appreciable retention of catalytic activity (227). A 13-vertex /oj iJ-hydridorhodacarborane has also been synthesized and demonstrated to possess catalytic activity similar to that of the icosahedral species (228). Ak-oxidation of closo- >(2- P((Z [) 2 - i- > l[l-Bih(Z, results in a brilliant purple dimer. This compound contains two formal Rh " centers linked by a sigma bond and a pak of Rh—H—B bridge bonds. A number of similar dimer complexes have been characterized and the mechanism of dimer formation in these rhodacarborane clusters have been studied in detail (229). 

The third group of studies involves attachment of the iron complexes to solid substrates in order to inhibit formation of bridged species. In a very early study, dioxygen was found to bind reversibly to haem diethyl ester embedded in a mixture of polystyrene and l-(2-phenylethyl)imidazole (Wang, 1958). 

Amphiphilic resin supported ruthenium(II) complexes similar to those displayed in structure 1 were employed as recyclable catalysts for dimethylformamide production from supercritical C02 itself [96]. Tertiary phosphines were attached to crosslinked polystyrene-poly(ethyleneglycol) graft copolymers (PS-PEG resin) with amino groups to form an immobilized chelating phosphine. In this case recycling was not particularly effective as catalytic activity declined with each subsequent cycle, probably due to oxidation of the phosphines and metal leaching. 

Covalent attachment chiral Co(salen) complexes to polystyrene and silica gave efficient and highly enantioselective catalysts for the hydrolytic kinetic resolution (HKR) of terminal epoxides, including epichlorohydrin. These systems provide practical solutions to difficulties with the isolation of reaction products from the HKR. Removal of the supported catalyst by filtration and repeated recycling was demonstrated with no loss of reactivity or enantioselectivity. The immobilised catalysts have been adapted to a... 

So far, few data are available which allow the comparison of differences in efficacy and selectivity of one catalytic system attached to different supports. As far as the TADDOLate complexes are concerned, no clear rules can be drawn. Polystyrene-based catalysts derived from (8) and (10) show similar enantioselectivities and reaction rates. Differences appear, however, when comparing them with a polystyrene-embedded dendritic ligand system, generated by co-polymerization from TADDOL-derivative (32) (Scheme 4.18) which is described in Section 4.3.2.1. Re-cydabihty seems to be easier for the dendritic catalyst and the enantioselectivity. 

Shibasaki et al. developed a polymer-supported bifunctional catalyst (33) in which aluminum was complexed to a chiral binaphtyl derivative containing also two Lewis basic phosphine oxide-functionahties. The binaphtyl unit was attached via a non-coordinating alkenyl Hnker to the Janda Jel-polymer, a polystyrene resin containing flexible tetrahydrofuran-derived cross-Hnkers and showing better swelling properties than Merifield resins (Scheme 4.19) [105]. Catalyst (33) was employed in the enantioselective Strecker-type synthesis of imines with TMSCN. 

R)-BINAP/l,2-diphenylethylenediamine ruthenium(II) complexes covalently attached to polystyrene (Scheme 4.32) promote the asymmetric hydrogenation of aromatic ketones and of a, yS-unsaturated ketones [125]. The catalysts (52) and (53) were reused at high substrate/catalyst molar ratio (S/C) of 2470 in 14 experiments. Remarkably, the enantiopurity of the products remained high after each run, constantly being in the range of 97 to 98% ee. 

The preparation of solids with covalently attached POM complexes is a serious and worthwhile research target because these materials might be expected to be rather stable to POM leaching in solutions. Many new materials of this type have been reported in the literature [16,49,74,137-143] however, catalytic studies on covalently boimd POMs still remain a rare event. In 1992, Judeinstein reported the first POM-polymer hybrid where a lacunary Keggin POM cluster was covalently linked to polystyrene or polymethacrylate backbone through Si-0 bonds [137]. This approach has been further developed by several research groups. 

A problem especially with oxidation catalysts is that the metals in their highest oxidation state tend to be less strongly associated with a support, so that the reaction conditions can lead to leaching of the metal complex from the support. To overcome this problem, microencapsulation, as an immobilization technique for metal complexes, has been introduced by Kobayashi and coworkers. In the microencapsulation method, the metal complex is not attached by covalent bonding but is physically enveloped by a thin film of a polymer, usually polystyrene. With this technique leaching of the metal can be prevented. In 2002, Lattanzi and Leadbeater reported on the use of microencapsulated VO(acac)2 for the epoxidation of allylic alcohols. In the presence of TBHP as oxidant, it was possible to oxidize a variety of substrates with medium to good yields (55-96%) and diastereomeric ratios (60/40 to >98/2) (equation 42). The catalyst is easily prepared and can be reused several times without significant loss in activity. 

It was indicated earlier that swelling limits resolution in solvent-developed negative resists. It was also intimated that swelling effects could be minimized if there were a sufficient polarity change between the exposed and non-exposed areas of the type mentioned in the previous discussion of the PBOCST system. A similar principle was utilized by Hofer et al., (145-146) at IBM, based on ion pair formation. The resist consists of a polystyrene polymer to which tetrathiofulvalene (TTF) units have been attached. When spun down with an acceptor such as CBr4, a complex is formed which, on irradiation, undergoes an electron transfer reaction to form an ion pair ... 

Asymmetric hydrosilylation of styrene with HSiCl3 catalyzed by a palladium complex of a chiral ferrocenylphosphine attached to cross-linked polystyrene support at 70 °C gives PhMeC HSiCl3 in quantitative yield with only 15.2% ee65. 

Complex 2 also proved valuable in attaching the ferrocene unit to chloromethylated polystyrene. Treatment of chloromethylated styrene (18% of the phenyl rings modified) with 2 under basic conditions afforded polymer 6. Polymer 7 was then prepared and found to have UV-Vis spectroscopic data analogous to monomer 4 and polymer 5. 

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