Xenon hexafluoride production

Electrochemical fluorination of pyridine in the presence of a source of fluoride ion gave 2-fluoropyridine in 22% yield (85M11). With xenon difluoride, pyridine formed 2-fluoropyridine (35%), 3-fluoropyridine (20%), and 2,6-difluoropyridine (11%) in a reaction unlikely to be a conventional electrophilic substitution. Xenon hexafluoride has also been used (76JFC179). With cesium fluoroxysulfate at room temperature in ether or chloroform, the major product was 2-fluoropyridine (61 and 47%, respectively). Some 2-chloropyridine was also formed in chloroform solution. In methanol the entire product was 2-methoxypyridine (90TL775). Fluorine, diluted with argon in acetic acid, gave a 42% yield of the 5-fluoro derivative of l-methyl-2-pyridone [82H( 17)429],... 

Preparation by hydrolysis of either xenon tetrafluoride or xenon hexafluoride. Oxidizing action,2 Xenic acid reacts readily with u/c-diols in neutral or alkaline solution the products are xenon (gas) and carboxylic acids. 

Like xenon hexafluoride or xenon tetrafluoride, krypton difluoride reacts with water, giving highly explosive hydrolysis products. The best way for disposing of krypton difluoride is to allow it to react with carbon tetrachloride (see caution note under xenon tetrafluoride procedure). 

All the xenon fluorides react with water to form various products. For example, in aqueous solution, xenon hexafluoride is first hydrolyzed to xenon oxide tetrafluoride, XeOp4, which is further hydrolyzed to xenon trioxide. The reactions are as follows ... 

The hexafluoride decomposes on heating also decomposed by UV radiation to lower fluorides and reacts with the inert gas xenon, forming a solid product, Xe(PtFe). It reacts with molecular oxygen to produce 02+PtFe The compound attacks glass at ordinary temperatures. 

In the preliminary communication [1] reporting the interaction of xenon with platinum hexafluoride, the adduct was given the empirical formula XePtF and was assumed to be a derivative of pentapositive platinum. Subsequent work has shown that although the gases may interact in a 1 1 ratio, the product usually contains more platinum and can have the composition Xe(PtFe)2. That the platinum in the xenon-platinum hexafluoride adduct Xe(PtFe) is in the +5 oxidation state has now been established. 

In their early studies of the oxidation of xenon by platinum hexafluoride Bartlett and Jha found [1] that the stoichiometry of the product of that spontaneous reaction varied between XePtF and Xe(PtFg)2. Chemical and physical evidence Indicated that the oxidation state of the platinum in Xe(PtFg)jj was +5. Pyrolysis of XeCPtFg), at 165°, yielded xenon tetra-fluorlde as the only identified volatile product, (xenon itself was not... 

These investigations have greatly clarified the nature of the products of the interaction of xenon with platinum hexafluoride. Presumably [XeF]+[PtFj] is produced as follows ... 

The reaction of xenon with platinum hexafluoride yields at least two distinct quinquevalent platinum products, XePtF, and Xe(PtFj)j. A third compound XePtjFij which is diamagnetic, is produced by heating the former. During continuing investigations of the reaction between xenon, fluorine, and platinum pentafluoride, at least two different compounds have been detected. The better characterized compound is produced when 1 1 molar ratios of xenon and platinum pentafluoride are employed in admixture with 80 p.s.i. 

Within a few weeks of the discovery ( > of xenon tetrafluoride by Claassen, Selig and Malm, they and their collaborators at the Argonne National Laboratory, had also prepared and characterized a difluoride < > and a hexafluoride (2 ). These compounds were soon confirmed in a number of other laboratories. Ali thee fluorides, which are white crystalline solids at room temperature are preparable from fluorine and xenon, the nature of the product depending upon the ratio of the reactants and the temperature, the tetrafluoride being thermally more stable than the hexafluoride... 

Xenon difluoride dissolves in water, yielding a solution which contains undissociated XeFa molecules which have a half-life of about 7 hours at 0°. It eventually hydrolyzes to yield the expected products, xenon, hydrogen fluoride, and oxygen. The hydrolysis reactions of the tetrafluoride and hexafluoride are somewhat more complicated. The addition of the stoichiometric amount of water to the hexafluoride results in the formation of xenon oxide tetrafluoride. Hydrolysis of either fluoride with an excess of water or acid yields in solution a stable xenon(VI) species, which has been shown to be hydrated xenon trioxide. Removal of the excess water leaves xenon trioxide as a solid residue. Inasmuch as this solid is an extremely sensitive explosive, such solutions must be handled with care. 

Xenon tetrafluoride was first prepared by heating a gaseous mixture of xenon and fluorine under moderate pressure. However, the product obtained by this method is always contaminated with xenon difluoride and hexafluoride, which are in chemical equilibrium with xenon tetrafluoride. Xenon tetrafluoride obtained in this way can be purified by subsequent chemical purification with arsenic pentafluoride." ... 

Bartlett s original reaction of xenon with PtF apparently yielded products other than the expected Xe PtF ". However, when xenon and PtF are reacted in the presence of a large excess of sulfur hexafluoride, Xe PtF " is apparently formed. Suggest the function of SF in this reaction. (See K. Seppelt, D. Lentz, Progr. Inorg. Chem., 1982, 29, 170.)... 

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