Covalent anchoring

Recently, Suzuki-type reactions in air and water have also been studied, first by Li and co-workers.117 They found that the Suzuki reaction proceeded smoothly in water under an atmosphere of air with either Pd(OAc)2 or Pd/C as catalyst (Eq. 6.36). Interestingly, the presence of phosphine ligands prevented the reaction. Subsequently, Suzuki-type reactions in air and water have been investigated under a variety of systems. These include the use of oxime-derived palladacycles118 and tuned catalysts (TunaCat).119 A preformed oxime-carbapalladacycle complex covalently anchored onto mercaptopropyl-modified silica is highly active (>99%) for the Suzuki reaction of p-chloroacetophenone and phenylboronic acid in water no leaching occurs and the same catalyst sample can be reused eight times without decreased activity.120... 

Several groups have recently shown (36,42,43,44) that photoanode materials can be protected from pRotoano3ic corrosion by an anodically formed film of "polypyrrole".(45) The work has been extended (46) to photoanode surfaces first"Treated with reagent that covalently anchors initiation sites for the formation of polypyrrole. The result is a more adherent polypyrrole film that better protects n-type Si from photocorrosion. Unlike the material derived from polymerization of I, the anodically formed polypyrrole 1s an electronic conductor.(45) This may prove ultimately important in that the rate of ionTransport of redox polymers may prove to be too slow... 

In 2002 Mehnert and co-workers were the first to apply SILP-catalysis to Rh-catalysed hydroformylation [74], They described in detail the preparation of a surface modified silica gel with a covalently anchored ionic liquid fragment (Scheme 7.7). The complex N-3-(3-triethoxysilylpropyl)-4,5-dihydroimidazole was reacted with 1-chlorobutane to give the complex l-butyl-3-(3-triethoxysilylpropyl)- 4,5-dihydroimidazolium chloride. The latter was further treated with either sodium tetrafluoroborate or sodium hexafluorophosphate in acetonitrile to introduce the desired anion. In the immobilisation step, pre-treated silica gel was refluxed with a chloroform solution of the functionalised ionic liquid to undergo a condensation reaction giving the modified support material. Treatment of the obtained monolayer of ionic liquid with additional ionic liquid resulted in a multiple layer of free ionic liquid on the support. 

SILC was also used without covalently anchoring the ionic liquid fragment to the silica support. In this case, [bmim][PF6] was simply added to silica in acetone together with the catalyst. [Rh(norbornadiene)(PPh3)2]PF6 and the solvent evaporated to yield the supported catalyst-philic phase. Catalyst evaluation on the hydrogenation of model olefins showed enhanced activity in comparison to homogeneous and biphasic reaction systems, in analogy to Davis s observations. Also... 

Figure 12. Schematic representation of the active peroxotungstate catalyst covalently anchored to silica via phosphoramide group [136].

Covalently Anchored Organometallic Complexes on Unmodified Silica... 

In 1962, solid-phase peptide synthesis was introduced, and described in detail in 1963.1171 This new synthetic principle was developed with the hope that it would simplify and accelerate the synthesis of peptides. The idea was to covalently anchor the C-terminal residue of a peptide to an insoluble support and then to assemble the remaining amino acids in a stepwise manner with activated amino acids while the peptide was in the insoluble solid phase, and finally to cleave the peptide from the solid support and liberate it into solution. The general methodology is shown in Scheme 6. 

Figure 15 Modified Pourbaix diagram for Ti02 illustrating the origins of pH-dependent band energetics and the pH-independent back-ET kinetics for covalently anchored dye species. The open circles are experimentally determined values of Ecb (combined electrochemical quartz microbalance and reflectance measurements). The driving force for the overall back reaction [coupled electron and proton transfer cf. Eqs. (10) and (11) for analogous reactions at Sn02] is pH dependent, but the driving force for the back ET in isolation [cf. Eq. (10)] is pH independent. (Data from Ref. 78.)...

One remarkable feature of all biological membranes is their flexibility—their ability to change shape without losing their integrity and becoming leaky. The basis for this property is the noncovalent interactions among lipids in the bilayer and the motions allowed to individual lipids because they are not covalently anchored to one another. We turn now to the dynamics of membranes ... 

A new optically active tetraazamacrocycle ligand, 27 ,37 -cyclohexano-1,4,7,10-tetra-azacyclododecane was covalently anchored on micelle-templated silicate (MTS) surface. The... 

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