Xenon reactions with

Trimethylarsine gives a 98% yield of trimethylarsine difluoride when treated with xenon difluoride [102] in fluorotrichloromelhane. and tnsfpentafluorophen-yl)arsine gives a 94% yield of tris(pentafluornphenyl)arsme difluoride after reaction with dilute fluorine in fluorotnchloromethane at 0 C [106] Other trivalent arsenic compounds have also been fluorinated with xenon difluoride [103] In addition, arsines have been oxidatively fluorinated by iodine pentafluoride [107] or electrochemically in 26-34% yield [108]... 

Carboxylic acids react with xenon difluoride to produce unstable xenon esters The esters decarboxylate to produce free radical intermediates, which undergo fluonnation or reaction with the solvent system Thus aliphatic acids decarboxylate to produce mainly fluoroalkanes or products from abstraction of hydrogen from the solvent Perfluoro acids decarboxylate in the presence of aromatic substrates to give perfluoroalkyl aromatics Aromatic and vinylic acids do not decarboxylate [91] (equation 51)... 

Xenon difluoride reaction with nitro enolates provides a useful entry into a wide variety of fluonnated synthetic intermediates [91 92] (equation 52)... 

A simple order of magnitude estimate of the rate constants for reaction with ethylene can be made for the high intensity ions in the 5-torr spectrum. Since the average reaction time, limited by neutralization or removal from the ion source is a few milliseconds (see section dealing with sampling conditions and section on ethylene in xenon) we can take 1 msec, as the half-life of these ions in 5-torr ethylene. This leads to k = 10-14 to 10-15 cc. molecule-1 sec.-1 as a rate constant for further reaction with ethylene. The value for 5a found by the kinetic treatment above was 8 X 10 -14. 

In another study (Ji8), it was found that graphite does not intercalate with neat XeF2 or with solutions of XeFa in acetonitrile. However, reaction with solutions of XeF2 in AHF led to copious xenon evolution, indicating that oxidation does take place, even at room temperature. Broad-line, F- and H-NMR spectra (Ell) showed the presence of both XeF2 and HF in the product, but no definite stoichiometry could be as-... 

XeFg +H2 O - XeOF4 + 2 HF Reaction with excess water produces xenon trioxide ... 

Xenon difluoride (or the tetrafluoride, or their mixtures) could not be caused to detonate by impact. Xenon difluoride and xenon tetrafluoride both may cause explosion in contact with acetone, aluminium, pentacarbonyliron, styrene, polyethylene, lubricants, paper, sawdust, wool or other combustible materials. Their vigorous reactions with ethanol, potassium iodate or potassium permanganate are not explosive, however. 

Interaction of the yellow hexafluoride with silica to give xenon tetrafluoride oxide must be interrupted before completion (disappearance of colour) to avoid the possibility of formation and detonation of xenon trioxide [1]. An attempt to collect the hexafluoride in fused silica traps at — 20°C after separation by preparative gas chromatography failed because of reaction with the silica and subsequent explosion of the oxygen compounds of xenon so produced [2],... 

We have recently prepared some new and very thermolabile CO- and N2 comPlexes derived from titanocene [1] or decamethyltitanocene [2], and have characterized them by their vibrational spectra. As well as "classical" matrix spectroscopy, we have used spectroscopy in liquid xenon (LXe). The application of chemistry and methodology indicates the decamethylsilicocene structure, which represents the first example of a stable jt-complex of divalent silicon [3]. Reaction with CO or N2 leads to the two title complexes [4] ... 

Radon difluoride is quantitatively reduced to elemental radon by water in a reaction which is analogous to the reactions of krypton difluoride and xenon difluoride with water. Complex salts of radon also hydrolyze in this fashion. 

O O In the early 1960s, Neil Bartlett, at the University of British Columbia, was the first person to synthesize compounds of the noble gas xenon. A number of noble gas compounds (such as XeF2, XeF4, XeFe, and XeOs) have since been synthesized. Consider the reaction of xenon difluoride with fluorine gas to produce xenon tetrafluoride. 

The most important application of organolithium reagents is their nucleophilic addition to carbonyl compounds. One of the simplest cases would be the reaction with the molecule CO itself, whose products are stable at room temperature. Recently, it was shown that a variety of RLi species are able to react with CO or f-BuNC in a newly developed liquid xenon (LXe) cell . LXe was used as reaction medium because it suppresses electron-transfer reactions, which are known to complicate the reaction . In this way the carbonyllithium and acyllithium compounds, as well as the corresponding isolobal isonitrile products, could be characterised by IR spectroscopy for the first time. 

The oxyfluoride, XeOF4 is a stable colorless liquid produced by the reaction of xenon hexafluoride with sodium nitrate ... 

Xenon also forms many fluoroanions and their salts, mostly prepared from xenon tetrafluoride and hexafluoride. Such compounds include Na+XeFs and Cs" XeF7- formed by reactions of xenon fluorides with sodium fluoride or cesium fluoride. The dicesium xenon octafluoride, Cs2XeFs, is a stable yellow solid that decomposes above 400°C. 

R.E. Ehrenkaufer, R.R. MacGregor, Synthesis of [ F]-perchloryl fluoride and its reactions with functionalized aryllithiums, Int. J. Appl. Radiat. Isot. 34(1983)613-615. R. Chirakal, G. Firnau, J.G. Schrobilgen, J. McKay, E.S. Garnett, The synthesis of [ F]xenon difluoride from [ F]fluorine gas, Int. J. Appl. Radiat. Isot. 35 (1984) 401-404. 

Pyridine is converted into perfluoropiperidine (82) in low yield by reaction with fluorine in the presence of cobalt trifluoride (50JCS1966) quinoline affords (83) under similar conditions (56JCS783). Perfluoropiperidine can be obtained electrochemically. This is useful, as it may be readily aromatized to perfluoropyridine by passing it over iron or nickel at ca. 600 °C (74HC(14-S2)407). Recently, pyridine has been treated with xenon difluoride to yield 2-fluoropyridine (35%), 3-fluoropyridine (20%) and 2,6-difluoropyridine (11%), but it is not likely that this is simply an electrophilic substitution reaction (76MI20500). 

Perfluoropropyl iodide (8) formed difluoroiodoperfluoropropane in 60% yield upon reaction with xenon difluoride at 20 C.21... 

The interaction of xenon difluoride with ethene at room temperature was investigated soon after xenon difluoride was discovered.26 The reaction mixture contained 1,2-difluoroethane (45%), 1,1-difluoroethane (35%) and 1,1,2-trifluoroethane (20%). 

The reaction of xenon difluoride with a series of cis- and trans-phenyl substituted alkenes was examined in detail. 1,1-Diphenylethene, l,1-diphenyl-2-fluoroethene and 1.1-diphenyl-propene form vicinal 1,2-difluoro derivatives in 65 95% yield in dichloromethane solution with hydrogen fluoride as the catalyst.29-32 Two possible mechanisms were discussed.33... 

To overcome problems associated with the removal of iodobenzene and its derivatives formed upon fluorination of arylalkenes and arylalkynes with (difluoroiodo)arenes, polymer-supported (difluoroiodo)arenes were proposed.139 With these agents, the separation procedures are reduced to filtration of the iodinated polymer. For this purpose popcorn polystyrene is io-dinated and then transformed into the difluoroiodide by treatment with xenon difluoride in the presence of hydrogen fluoride in dichloromelhane at 25 C. The amount of active fluorine bonded to iodine atoms on the polymer support is estimated by iodometric titration. The reactions with phenyl-substituted alkenes result in rearranged gew-difluorides. The procedure provides the same fluorination products as with (difluoroiodo)benzenc (see Section 4.13.) but in much higher yields, e.g. PhCF2CH2Ph (96%), PhCF2CH(Me)Ph (95%). PhCH2CF2H (86%), and l,l-difluoro-2-phenylcyclopentanc (91 %). 

Reaction of Xenon Difluoride with Butadiene (2, R = H) Typical Procedure 44... 

Fhiorination of aromatics. The reagent reacts with toluene to form benzyl fluoride as the major product ( 65% yield). It is also useful for fluorination of phenols- and of alkyl ethers of phenols the or/Ao-isomcr is formed as the major product. Reactions with this reagent thus differ from those with xenon difluoride, which generally favors formation of paro-isomers. 

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