J. Slivnik

Syntheses and vibrational spectra of xenon(VI) fluorozirconate(IV) and xenon(VI) fluorohafnate(IV)

Abstract Liquid xenon difluoride at 140°C does not react with zirconium or hafnium tetrafluorides, neither does liquid xenon hexafluoride at 60°C. Therefore reactions between the corresponding hydrazinium fluorometalates or ammonium fluorometalates and xenon difluoride and xenon hexafluoride, respectively, were carried out. N 2 H 6 ZrF 6 and N 2 H 6 HfF 6 react with xenon difluoride at 60°C again yielding only the corresponding tetrafluorides, while the analogous reaction with (NH 4 ) 2 ZrF 6 and (NH 4 ) 2 HfF 6 proceeds at 170°C yielding the corresponding ammonium pentafluorometalates, which are stable and do not react further with excessive xenon difluoride up to 200°C. The reaction between N 2 H 6 ZrF 6 or N 2 H 6 HfF 6 and xenon hexafluoride proceeds at room temperature yielding a series of thermally unstable compounds of the type mXeF 6 .MF 4 (M = Zr, Hf) where m ⩽ 6. The final products which are stable at room temperature are XeF 6 .MF 4 (M = Zr,Hf). Spectroscopic evidence suggests that these compounds are salts of a XeF + 5 cation squashed between a polymeric anion of the type (MF 5 ) x- x .

Syntheses and vibrational spectra of xenon(VI) fluorogallate, xenon(VI) fluoroaluminate and xenon(VI) fluoroindate

Abstract Liquid xenon difluoride at 140°C does not react with aluminium, gallium, and indium trifluorides, neither does liquid xenon hexafluoride at 60°C. Therefore the reactions between the corresponding hydrazinium fluorometalates (N 2 H 6 AlF 5 , N 2 H 6 GaF 5 and N 2 H 5 InF 4 ) and XeF 2 and XeF 6 were carried out. N 2 H 6 AlF 5 , N 2 H 6 GaF 5 and N 2 H 5 InF 4 react with XeF 2 at 60°C (at 25°C in the case of indium) yielding only the corresponding trifluorides, while the reaction with XeF 6 proceeds at room temperature (at - 25°C in the case of indium) yielding XeF 6 .2AlF 3 , XeF 6 .GaF 3 and xenon(VI) fluoroindate(III) contaminated with indium trifluoride. Spectroscopic evidence suggests that these compounds are salts of the XeF + 5 cation squashed between polymeric anions of the type (M 2 F 7 ) x- x or (MF 4 ) x- x .

Some photosyntheses with elemental fluorine

Abstract The photochemical reaction between fluorine and xenon was investigated in gas-gas and liquid (F 2 ) - solid (Xe) systems. In both cases xenon difluoride, xenon tetrafluoride or xenon hexafluoride could be obtained. Until now the photochemical synthesis of XeF 2 (1,2,3) and XeF 4 (4) from gaseous mixtures only was described and the formation of XeF 6 within photochemical reaction was not known. Similarly the reaction in the system F 2 (liquid) - Xe (solid) was not published. The conditions of photochemical synthesis of XeF 6 from gaseous mixtures are described. The photochemical reactions of solid Xe, XeF 2 and XeF 4 with liquid fluorine are discussed.