Silver hexafluorophosphate

Anhydrous silver hexafluorophosphate [26042-63-7] AgPF, as well as other silver fluorosalts, is unusual in that it is soluble in ben2ene, toluene, and xylene and forms 1 2 molecular crystalline complexes with these solvents (91). Olefins form complexes with AgPF and this characteristic has been used in the separation of olefins from paraffins (92). AgPF also is used as a catalyst. Lithium hexafluorophosphate [21324-40-3] LiPF, as well as KPF and other PF g salts, is used as electrolytes in lithium anode batteries (qv). 

The silver fluorocomplexes, ie, silver hexafluoroantimonate [26042-64-8], AgSbF silver hexafluorophosphate [26042-63-7], AgPF silver tetrafluoroborate [14104-20-2], AgBF and other salts such as silver trifluoromethane sulfonate [2923-28-6], CF SO Ag, and silver trifluoroacetate [2966-50-9], CF COOAg, play an important role in the synthesis of organic compounds and have gained potential industrial importance. 

These compounds perform a dual function in synthesis procedures. The introduction of a complex anion assists in the stabilization of the desired product and the generation of unique intermediates by chloride displacement, eg, silver hexafluorophosphate, AgPF, forms adducts with neutral diamagnetic organometaHics which can act as controUed sources of highly reactive cations (29). Silver hexafluoroantimonate, AgSbF, is an electrophilic... 

Silver hexafluorophosphate (76 mg, 0.3 mmol) is added to a solution of Re(CO)3(bipy)Br (53.6mg, O.lOmmol) in dichloromethane (15mL). The mixture is stirred for 30 min, filtered into a cold flask, and concentrated to a small volume by applying vacuum. Light petroleum ether at 0 °C is added to precipitate a fine yellow powder. The solvent is decanted and the product dried on the vacuum line yields 36.3 mg, 0.07 mmol (69%). 

The reactions of chlorosilicon and chlorogermanium transition metal complexes with silver hexafluoroantimonate, as well as with silver tetrafluoroborate or silver hexafluorophosphate. 

Gevorgyan et al. also observed alkyl migration while studying the cyclization of substituted allenones in the presence of various metal salts. While again not the best catalysts, silver hexafluorophosphate or triflate could be used in toluene or dichlor-omethane, giving substituted furans in high yields (Scheme 3.56).84... 

When the rigid tridentate ligand l,3,5-tri-3-pyridyl-2,4,6-tri-/)-tolyl-benzene (3) was reacted with silver(I) triflate or silver hexafluorophosphate, cage-like... 

Materials. (Bicyclo[2.2.1]hepta-2,5-diene) rhodium(I) chloride dimer and silver hexafluorophosphate were purchased from Strem Chemical the rhodium complex was recrystallized from acetone prior to use. All silanes (Aldrich) were distilled under a nitrogen atmosphere, freeze-thaw degassed and stored under a nitrogen atmosphere. 4-cyclopentene-l,3-dione (CPDK) from Aldrich was recrystallized from diethyl ether and stored in the dark under a nitrogen atmosphere at -40°C. All solvents were distilled under nitrogen from appropriate drying agents immediately prior to use. 

In the first study 2,2-dimethoxy-2-phenyl acetophenone was photolysed at 366 ran in n-butylvinyl ether in the presence of di-p-tolyl iodonium hexafluorophosphate as oxidising salt. The free radicals produced in the photolysis were transformed into cationic active species for the polymerisation of the vinyl ether by the electron transfer to the iodonium ion. In the second report, various radical sources were photolysed in the presence of the monomer and silver hexafluorophosphate, the latter acting as one-electron oxidant. 

The reaction of 1 -hexene with phenylselenenyl hexafluorophosphate (PhSePF6) in toluene which resulted in the formation of the seleniranium ion (92) has been reported <75TL399l>. This seleni-ranium ion (92) was also shown to be an intermediate in the reaction of 2-bromohexyl phenyl selenide (93) with dimethylsulfoxide in the presence of silver hexafluorophosphate (AgPF6) and triethylamine which leads to the formation of a-phenylselenoketone (94) (Scheme 19) <78TL226i>. 

Smets and co-workershave examined in depth direct and radical-induced cationic photopolymerizations. The latter mechanism is interesting and the authors quote as an example the cationic polymerization of butyl vinyl ether in the presence of phenylazotriphenylmethane and a silver salt with a non-nucleophilic anion, such as silver hexafluorophosphate. Scheme 5 shows initial radical production to give a triphenylmethane radical followed by electron transfer with the silver salt to give a complex. Unfortunately, such a free-radical process G. Smets, A. Aerts, and J. Van Erum, Polym. J., 1980, 12, 539. 

Following the well-known Pinner synthesis of imidates by the reaction of nitriles with alcohols, there has been considerable interest in recent years in treating a nitrile bond within the coordination sphere of metal ions with water or alcohols. It has been suggested that the initial step consists of nucleophilic attack of an external or coordinated hydroxide or alkoxide anion on the nitrile carbon atom. A number of imidate complexes have been isolated from the reactions of 2-cyanopyridine with metal [Cu", Ni , Co" and Fe"] salts in alcohols, of frans-PtMeClL with pentafluorobenzonitrile and silver hexafluorophosphate in alcohols," and of o-cyanobenzylplati-num complexes. "... 

A series of imino ether complexes with the typical composition [PtMeLj (NH=C(OMe)C5F4-C(OMe)=NH)PtMeL2][(BF4)2] (where L = PMe2Ph) have been synthesized" by the reactions of irans-PtMeClL2 with pentafluorobenzonitrile and silver hexafluorophosphate in methanol (alcohol). The comparative role of PtMe and PtCF3 in such reactions has been discussed " to elucidate the mechanism of such reactions." The preparation of iridium imino ether complexes has been reported by a similar route. 

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