Zeolites allyl cations

The allyl cation has never been characterized as a persistent species in solution. If prepared, it would be the smallest carbenium ion universally accepted to have been formed in condensed media (this title has for many years been held by the isopropyl cation). No allyl cation derivatives, e.g., 10, were observed in a 1990 report of a CAVERN study of butadiene on HY and HZSM-5 (104). The same year, Hutchings reported a flow reactor study of allyl alcohol on HZSM-5 (105) and Gorte (106) reported a TPD study of allyl alcohol on the same zeolite. Hutchings and co-workers found that allyl alcohol had two reaction paths, one in which propanal was formed and another that formed hydrocarbons. The latter route was proposed to proceed through an allyl cation intermediate, but no claim for its persistence or spectroscopic observation was made or implied by Hutchings. Gorte... 

In early 1993, Haw and co-workers (107) reported in situ studies of allyl alcohol-/-13C on HZSM-5 and CsHX. No persistent carbenium ions were observed, but 1,3 label exchange was observed for the alcohol on the weakly acidic zeolite. We interpreted this as support for a transient allyl cation. The low stability of this cation was invoked to explain the failure to observe this species as a persistent species. Downfield signals observed in that study were attributed to the formation of propanal. Later in 1993, Biaglow, Gorte, and White (BGW) (108) reported similar studies conducted at different loadings and assigned a downfield resonance (variously reported at 216 and 218 ppm by BGW) to the allyl cation in HZSM-5. 

In 1994, Buzek et al. (109) reported that the allyl cation could be prepared from a variety of halide precursors, e.g., allyl chloride or cyclopropyl bromide, on SbF5 at cryogenic temperature, based on the infrared spectrum of the products. Those workers challenged BGW s claim of the persistent allyl cation based on the discrepancy between the isotropic 13C shift in the zeolite and that calculated at MP2/6-31G. This was one of the first examples of the use of chemical shift calculations to interpret (and in this case challenge) an NMR study of a species on a solid acid. 

ITQ-2, a novel zeolitic structure prepared by swelling and delaminating a MWW precursor, has been studied by IR spectroscopy. The same precursor yields, when calcined, the zeolite MCM-22. Bronsted acidity has been measured as the propensity either to engage in H-bonds or to transfer the proton to unsaturated hydrocarbons. Comparison with MCM-22 shows that dealumination accompanies the process of delamination, but no appreciable change in residual Bronsted acidity takes place. Reaction of propene with Bronsted sites to branched oligomers occurs mainly on the external surface. Oligomers show no tendency to evolve to allylic cationic species, in contrast with MCM-22. 

Natural compounds are also applied as chiral ligands in enantioselective homogeneous metallo-catalysts. A classical example is the Sharpless epoxidation of primary allylic alcohols with tert-butyl hydroperoxide [37]. Here the diethyl ester of natural (R,R)-(+)-tartaric acid (a by-product of wine manufacture) is used as bi-dentate ligand of the Ti(iv) center. The enantiomeric excess is >90%. The addition of zeolite KA or NaA is essential [38], bringing about adsorption of traces of water and - by cation exchange - some ionization of the hydroperoxide. 

In 1993, Blatter and Frei [34] extended the Aronovitch and Mazur [28] photo-oxidation into zeolitic media, which resulted in several distinctive advantages as described below. Irradiation in the visible region (633 nm) of zeolite NaY loaded with 2,3-dimethyl-2-butene, 16, and oxygen resulted in formation of allylic hydroperoxide, 17, and a small amount of acetone. The reaction was followed by in situ Fourier-transform infrared (FTlR) spectroscopy and the products were identified by comparison to authentic samples. The allylic hydroperoxide was stable at - 50°C but decomposed when the zeolite sample was warmed to 20°C [35]. In order to rationalize these observations, it was suggested that absorption of light by an alkene/Oi charge-transfer complex resulted in electron transfer to give an alkene radical cation-superoxide ion pair which collapses... 

POMs can he immobilized onto anion-exchange resins and surface-modified metal oxides with quaternary ammonium cation- or amino-functional groups via anion-exchange. Jacobs and coworkers tethered Venturello s catalyst [P04(W0(02)2)4]3-on a commercially available nitrate-form resin with alkylammonium cations and have carried out the epoxidation of allylic alcohols and terpenes with this supported catalyst [166, 167]. The regio- and diastereoselectivity of the parent homogeneous catalysts were preserved in the supported catalyst. For bulky alkenes, the reactivity of the POM catalyst was superior to that of Ti- 3 zeolite with a large pore size. The catalytic activity of the recycled catalyst was maintained completely after several cycles. 

Figure 28 Cation-alkene interaction within a supercage of cation-exchanged Y-zeolite may control the conformations of allylic hydrogens. For allylic hydrogen abstraction, Ha and Hb should be parallel to the tt orbital (see top).

Electron donor-acceptor centres have been identified in zeolites and their relevance to catalysis discussed. Shih has found the cation radical C5H8 +, on H-mordenite treated with cyclopentene, to react to give a carbonium ion and an allylic radical ... 

Injection of ethene at 150°C or above produces a new infrared band at about 1500 cm (Figure 6), which is in the frequency range characteristic of partially unsaturated C-C bonds. Alkanes are detected in the gas phase above zeolites heated in the presence of ethene, and an intense absorption band appears in the ultraviolet-visible spectrum of ZSM-5 on heating in ethene to 100°C at 280 nm which has been attributed to an allyl carbenium cation (refs. 

Oxidation. Epoxidation of chiral allylic alcohols with urea-H Oj catalyzed by ZSM-5 zeolite (titanium silicate-1) and ene-type hydroperoxidation of alkenes photosensitized by thiazine dye cation-exchanged zeolites have been reported. In the latter reaction, only one product is formed. 

In 1996, Li and Ramamurthy reported the use of zeoHtes to enhance the regioselectivity in the O2 ene-reaction. In contrast to the reaction in solution, in which the cis effect applies, a remarkable twin selectivity is observed in zeolites. This was mechanistically rationalized in terms of coordination of the double bond to the Na+ ion in the zeoHte (cation-ti interaction), which polarizes the double bond for Markovnikov selectivity and induces conformational constraint in the allylic cis substituents (Figure 8.8). The latter effect disfavors stericaUy the formation of the cis perepoxide-like structure or prevents a perpendicular orientation of the ds-hydrogens for coordination and abstraction. Complications may arise from the formation of tertiary hydroperoxides from /one-hydrogen abstraction, which may selectively decompose on prolonged irradiation this falsifies the regioselectivity. ... 

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