On the preparation of fluorine-18 labelled XeF(2) and chemical exchange between fluoride ion and XeF(2).
A recent report claims to have prepared [18F]XeF2 by exchange between a large stoichiometric excess of XeF2 and no-carrier-added 18F-, as salts of the [2,2,2-crypt-M+] (M = K or Cs) cations, in CH2Cl2 or CHCl3 solvents at room temperature. Attempts to repeat this work have proven unsuccessful and have led to a critical reinvestigation of chemical exchange between fluoride ion, in the form of anhydrous [N(CH3)4][F] and [2,2,2-crypt-K][F], and XeF2 in dry CH2Cl2 and CH3CN solvents. It was shown, by use of 19F and 1H NMR spectroscopies, that [2,2,2-crypt-K][F] rapidly reacts with CH3CN solvent to form HF2-, and with CH2Cl2 solvent to form HF2-, CH2ClF, and CH2F2 at room temperature. Moreover, XeF2 rapidly oxidizes 2,2,2-crypt in CH2Cl2 solvent at room temperature to form HF and HF2-. Thus, the exchange between XeF2 and no-carrier-added 18F- reported in the prior work arises from exchange between XeF2 and HF/HF2-, and does not involve fluoride ion. However, naked fluoride ion has been shown to undergo exchange with XeF2 under rigorously anhydrous and HF-free conditions. A two-dimensional 19F-19F EXSY NMR study demonstrated that [N(CH3)4][F] exchanges with XeF2 in CH3CN solvent, but exchange of HF2- with either XeF2 or F- is not detectable under these conditions. The exchange between XeF2 and F- is postulated to proceed by the formation of XeF3- as the exchange intermediate.
Vasdev
Neil
N
Department of Chemistry, McMaster University, Hamilton, Ontario L8S 4M1, Canada.
Pointner
Bernard E
BE
Chirakal
Raman
R
Schrobilgen
Gary J
GJ
D004355:Drug Stability; D005459:Fluorides / Q000737:chemistry*; D005462:Fluorine Radioisotopes / Q000737:chemistry*; D007553:Isotope Labeling / Q000379:methods*; D007700:Kinetics; D008752:Methylene Chloride / Q000737:chemistry; D017680:Potassium Compounds / Q000737:chemistry; D019275:Radiopharmaceuticals / Q000138:chemical synthesis; D014978:Xenon / Q000737:chemistry*
D005462:Fluorine Radioisotopes; D017680:Potassium Compounds; D019275:Radiopharmaceuticals; D014978:Xenon; D008752:Methylene Chloride; C048007:xenon fluoride; C033320:potassium fluoride; D005459:Fluorides