Hexafluorophosphate Links

In a very recent study, it has been demonstrated116 that zinc 5,15-bis(3,5-di-tert-butylphenyl)-porphyrin (13) without any activating halogen atoms at the chromophore can be directly linked in a very simple oxidative coupling reaction with silver(I) hexafluorophosphate to a mixture of porphyrin dimers, trimers and tetramers. The separation of the product mixture was achieved by gel-permeation chromatography based on the molecular weights of the oligomers. The dimer when re-exposed to the same reaction conditions yielded 25% of the tetramer.116... 

The derivative 90 was obtained by condensation of the purpurin-18-A-hexylimide-17-propionic acid with aminolactose heptaacetate in the presence of benzotriazol-l-yloxy-tris(dimethylamino)phosphonium hexafluorophosphate (BOP) followed by the deacetylation procedure. The lactose-photosensitiser conjugate linked by an ethylene moiety was also prepared by following a similar approach. The purpurin-18-methyl ester 81 was converted into /V-(3-iodobenzyl)/ /evo-purpurin-18-7V-hexylimide-17-propionic ester by hydrogenation over Pd/C followed by reaction with 3-iodo-benzylamine. Afterwards, the propargyllactose heptaacetate reacted with A-(3-iodobenzyl)rMeio-purpurin-18-A-hexylimide-l 7-propionic ester in the presence of tris(dibenzylidieneacetone)dipalladium(0) (Pd2-dba3) which, after deacetylation conditions, afforded the derivative 89 (Fig. 9).68... 

In their test system, the researchers used the ionic liquid l-butyl-3-methylimidazol-ium hexafluorophosphate (bmim)(PF6), which is stable in the presence of oxygen and water, with naphthalene as a low-volatility model solute. Spectroscopic analysis revealed quantitative recovery of the solute in the supercritical CO2 extract with no contamination from the ionic liquid. They found that CO2 is highly soluble in (bmim)(PF6) reaching a mole fraction of 0.6 at 8 MPa, yet the two phases are not completely miscible. The phase behavior of the ionic liquid-C02 system resembles that of a cross-linked polymer-solvent system (Moerkerke et al., 1998), even though... 

TEMPO Tentagel Teoc TES Tf TFA TFFH 2,2,6,6-tetramethyl-l-piperidinyloxy PEG-grafted cross-linked polystyrene 2-(trimethylsilyl)ethoxycarbonyl triethylsilane trifluoromethanesulfonyl trifluoroacetic acid tetramethylfluoroformamidinium hexafluorophosphate, [(Me2N)2CF] [P F ]... 

With these anthracene-linked dimeric cinchona-PTCs, the Najera group investigated the counterion effect in asymmetric alkylation of 1 by exchanging the classical chloride or bromide anion with tetrafluoroborate (BF4 ) or hexafluorophosphate (PF6-) anions (Scheme 4.10) [17]. They anticipated that both tetrafluoroborate and hexafluorophosphate could form less-tight ionic pairs than chloride or bromide, thus allowing a more easy and rapid complexation of the chiral ammonium cation with the enolate of 1, and therefore driving to a higher enantioselectivity. However, when... 

The condensation of l,l -bis(chlorocarbonyl)-cobalticinium chloride (82) with various phenols and alcohols followed by chromatographic purification and excess ammonium hexafluorophosphate gave the ester-linked polycobalticinium macrocycles (83)-(86) (Scheme 28). The first... 

Another example of dissolving metals in ILs is linking a complex to an IL. Tan et al. synthesized a series of salen Mn(III) complexes functionalized by l-propylamine-3-methylimidazolium tetrafluoroborate ILs [180], Iida et al. have reported an interesting set of Ag-based ILs, bis(/V-2-c(hylhcxylethylenediamine) silver nitrate, [Ag(eth-hex-en)2]N03, and bis(/V-hex yI et hyI enediamine)silvertl) hexafluorophosphate, [Ag(hex-en)2]PF6 [181], which are precursors for silver nanoparticles (Fig. 8). 

Figure 2.2 Modern solid phase peptide synthesis. Process begins with a-N terminal Fmoc deprotection of resin bound C-terminal amino acid residue with piperidine (mechanism illustrated). Peptide link formation follows (typical solvent Al-methylpyrrolidone [NMP]) by carboxyl group activation with dicyclohexylcarbodiimide (DCC) (mechanism illustrated) in presence of hydroxybenzotriazole (HOBt). HOBt probably replaces DCC as an activated leaving group helping to reduce a-racemization during peptide link formation. Other effective coupling agents used in place of DCC/HOBt are HBTU 2-(lH-benzotriazol-l-yl)-l,l,3,3-tetramethyluronium hexafluorophosphate Py-BOP benzotriazole-l-yl-oxy-tns-pyrrolidino-phosphonium hexafluorophosphate. The Process of a-N deprotection, and peptide link formation, continues for as many times as required (n-times), prior to global deprotection and resin removal.

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. 

A gel electrolyte consists of an ion conducting polymer, such as polyoxyethylene or a polymer with polyoxyethylene segment, and an ion source. Hexafluorophosphate or tetrafluoroborate salts of lithium are commonly employed as the ion source. Other common components of the gel are liquid electrolytes like ethylene carbonate or propylene carbonate, both of which are used to increase the overall ion conductivity. Cross-linking agents, such as photo cross-linked acrylates or polyurethanes, can be incorporated to improve the mechanical stability of gel electrolytes. 

Simple condensation reactions of cobalticinium hexafluorophosphate activated ester and 1,1 -bis(chlorocarbonyl)cobalticinium chloride with various amines produced new acyclic tripodal, and 1,1 -bis-substituted amide-linked cobalticinium ligands in very good yields. (Schemes 1 and 2). 

A series of diamide-based cryptands derived from bis(m-phenylene)-[32]crown-10 have been synthesized to complex divalent salts such as paraquat (N,N-dimethyl-4,4 -bipyridinium) dichloride. The synthetic project started from the observation that readily prepared bicyclic crown ether 23 containing two 1,3,5-phenylene units linked by three tetra(ethyleneoxy) units forms a pseudorotaxane-like inclusion complex with Af,Af-dimethyl-4,4-bipyridinium bis(hexafluorophosphate), with an association constant /fa = 6.1 X 1() M that is 100-fold greater than that of the analogous simple crown ether. On this basis, additional anion-binding moieties, such as isophthalamide or 2,6-pyridinedicarboxamide unit, were intfoduced in the third chain of the cryptand receptor. The anion-assisted complexation of bypyridinium dications was analyzed by a combination of different techniques ( H NMR,... 

Endo, T., Kato, T., Tozaki, K. and Nishikawa, K., Phase behaviors of room tenperature ionic liquid linked with cation conformational changes 1-Butyl-3-methylimidazolium hexafluorophosphate, J. Phys. Chem. B 114 (1), 407 11 (2010). 

---