The XeOSeF5+ cation has been synthesized for the first time and characterized in solution by 19F, 77Se and 129Xe NMR spectroscopy and in the solid state by X-ray crystallography and Raman spectroscopy with AsF6- as its counter anion. The X-ray crystal structures of the tellurium analogue and of the Xe(OChF5)2 derivatives have also been determined: [XeOChF5][AsF6] crystallizes in a tetragonal system, P4/n, a = 6.1356(1) ?, c = 13.8232(2) ?, V = 520.383(14) ?3, Z = 2 and R1 = 0.0453 at -60 oC (Te) and a = 6.1195(7) ?, c = 13.0315(2) ?, V = 488.01(8) ?3, Z = 2 and R1 = 0.0730 at -113 oC (Se); Xe(OTeF5)2 crystallizes in a monoclinic system, P21/c, a = 10.289(2) ?, b = 9.605(2) ?, c = 10.478(2) ?, b = 106.599(4) o, V = 992.3(3) ?3, Z = 4 and R1 = 0.0680 at -127 oC; Xe(OSeF5)2 crystallizes in a triclinic system, R , a = 8.3859(6) ?, c = 12.0355(13) ?, V = 732.98(11) ?3, Z = 3 and R1 = 0.0504 at -45 oC. The energy minimized geometries and vibrational frequencies of the XeOChF5+ cations and Xe(OChF5)2 were calculated using density functional theory, allowing for definitive assignments of their experimental vibrational spectra.
Revised: February 28, 2002 |
Published: February 28, 2001
Citation
Fir B.A., H. Mercier, H. Mercier, J.P. Sanders, D.A. Dixon, and G.J. Schrobilgen. 2001.Structural and Theoretical Studies of Xe(OChF5)2 and [XeOChF5][AsF6] (Ch = Se, Te).Journal of Fluorine Chemistry 110, no. 2:89-107.PNNL-SA-34382.