Hexafluorophosphate Subject

The choice of the anion ultimately intended to be an element of the ionic liquid is of particular importance. Perhaps more than any other single factor, it appears that the anion of the ionic liquid exercises a significant degree of control over the molecular solvents (water, ether, etc.) with which the IL will form two-phase systems. Nitrate salts, for example, are typically water-miscible while those of hexaflu-orophosphate are not those of tetrafluoroborate may or may not be, depending on the nature of the cation. Certain anions such as hexafluorophosphate are subject to hydrolysis at higher temperatures, while those such as bis(trifluoromethane)sulfonamide are not, but are extremely expensive. Additionally, the cation of the salt used to perform any anion metathesis is important. While salts of potassium, sodium, and silver are routinely used for this purpose, the use of ammonium salts in acetone is frequently the most convenient and least expensive approach. 

Inter- and intramolecular hetero-Diels-Alder cycloaddition reactions in a series of functionalized 2-(lH)-pyrazinones have been studied in detail by the groups of Van der Eycken and Kappe (Scheme 6.95) [195-197]. In the intramolecular series, cycloaddition of alkenyl-tethered 2-(lH)-pyrazinones required 1-2 days under conventional thermal conditions involving chlorobenzene as solvent under reflux conditions (132 °C). Switching to 1,2-dichloroethane doped with the ionic liquid l-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6) and sealed-vessel microwave technology, the same transformations were completed within 8-18 min at a reaction temperature of 190 °C (Scheme 6.95 a) [195]. Without isolating the primary imidoyl chloride cycloadducts, rapid hydrolysis was achieved by the addition of small amounts of water and subjecting the reaction mixture to further microwave irradia-... 

While on the subject of polymerization media, there is also a report of CCT in ionic liquids.127 l-Butyl-3-methylimidazolium hexafluorophosphate is a room-temperature ionic liquid. Although such liquids have been found to be excellent solvents for a number of chemical transformations, there are few reports of polymerizations.128 Nonetheless, Con-mediated cata-... 

Rattray and Sutton s binuclear complex 10.42 contains Pd -atoms. Palladium(O) complexes resulted, however, in spontaneous elimination of N2 to give arylpalladi-um complexes (Kikukawa and Matsuda, 1977 Rattray and Sutton, 1978). Yet, Mat-suda s group (Yamashita et al., 1980) was able to obtain (aryldiazenido)palladium(O) complexes by adding two equivalents of an arenediazonium tetrafluoroborate or hexafluorophosphate to a suspension of [[P(C6H5)3)4Pd j in dichloromethane at — 78°C and allowing the mixture to warm to room temperature. Scheme (10-17) demonstrates that a mixture of the aryldiazenido and the aryl complex of Pd is formed. The aryldiazenido complex is subject to dediazoniation at room temperature. UV-irradiation facilitates this dediazoniation. Only in the case of 4-methoxy-benzenediazonium hexafluorophosphate was it possible to isolate the aryldiazenido complex and to identify it by elemental analysis, NMR, and IR spectroscopy. 

Topics which have formed the subjects of reviews this year include excited state chemistry within zeolites, photoredox reactions in organic synthesis, selectivity control in one-electron reduction, the photochemistry of fullerenes, photochemical P-450 oxygenation of cyclohexene with water sensitized by dihydroxy-coordinated (tetraphenylporphyrinato)antimony(V) hexafluorophosphate, bio-mimetic radical polycyclisations of isoprenoid polyalkenes initiated by photo-induced electron transfer, photoinduced electron transfer involving C o/CjoJ comparisons between the photoinduced electron transfer reactions of 50 and aromatic carbonyl compounds, recent advances in the chemistry of pyrrolidino-fullerenes, ° photoinduced electron transfer in donor-linked fullerenes," supra-molecular model systems,and within dendrimer architecture,photoinduced electron transfer reactions of homoquinones, amines, and azo compounds, photoinduced reactions of five-membered monoheterocyclic compounds of the indigo group, photochemical and polymerisation reactions in solid Qo, photo- and redox-active [2]rotaxanes and [2]catenanes, ° reactions of sulfides and sulfenic acid derivatives with 02( Ag), photoprocesses of sulfoxides and related compounds, semiconductor photocatalysts,chemical fixation and photoreduction of carbon dioxide by metal phthalocyanines, and multiporphyrins as photosynthetic models. 

Finally, it should be said that the above-discussed osmotic pressure-forced retention of one of the components of a mixture subjected to separation according to size exclusion mechanism does not exclude the possibility of true retention-type solute/sorbent interactions. Hypercrosslinked polystyrene may well enter attractive interactions with soft and lipophilic (chaotropic [163]) anions, such as sulfide, thiosulfate, rhodanide, perchlorate, tetrafluoroborate, and hexafluorophosphate. Also, some cations such as silver, copper, and mercury may interact with the aromatic 71-systems of the polystyrene matrix, which will retard the movement of the ions. These interactions may contribute to the separation of the ions from their stiU larger competing ions, but they may also be counterproductive to the size exclusion effect and deteriorate the separation of the retarded ions from smaller species. 

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