TY - JOUR
T1 - The XeN(SO2F)2 + and F[XeN(SO2F)2]2 + Cations
T2 - Syntheses, Raman and Multinuclear Magnetic Resonance Studies of the AsF6 and Sb3F16 Compounds, and X-ray Structure of XeN(SO2F)2 +Sb3F16-
AU - Faggiani, Romolo
AU - Kennepohl, Dietmar K.
AU - Lock, Colin J.
AU - Schrobilgen, Gary J.
PY - 1986/2/1
Y1 - 1986/2/1
N2 - Like its XeF2 precursor, the Xe-N-bonded FXeN(SO2F)2molecule exhibits fluoride ion donor properties that, in the present work, have resulted in the syntheses of adducts having the stoichiometries FXeN(SO2F)2.AsF5, FXeN(SO2F)2-3SbF5, and 2FXeN-(SO2F)2*AsF5. All compounds have been enriched to 30% with 15N and studied by 15N, 19F, and 129Xe NMR spectroscopy and Raman spectroscopy. The spectroscopic studies have shown the above stoichiometries to be consistent with the predominantly ionic formulations XeN(SO2F)2 +AsF6“, XeN(SO2F)2 +Sb3F16 -, and F[XeN(SO2F)2]2 +AsF6 -. In general, the cations are thermally less stable than their fluorine analogues, XeF+and Xe2F3 +. The crystal structure of XeN(SO2F)2 +Sb3F16~ has been obtained at -64 °C from three-dimensional X-ray data. [Bis(fluorosulfuryl)amido]xenon(II) hexadecafluorotriantimonate(V) crystallizes in the monoclinic system, space group P21/c, with four molecules in a unit cell of dimensions a = 10, 320 (2) Å, b = 10.642 (2) Å, c = 18.167 (3) Å, and β = 108, 94 (1)°. The structure was solved by the heavy-atom method and refined by least-squares and Fourier methods to a final R factor of 0.061 for 2376 observed (F > 0) reflections. The structure analysis has established the existence of discrete XeN(SO2F)2 +Sb3F16“ molecules and shows that the XeN(SO2F)2 +cation is Xe-N bonded and that the Xe-N bond (2.02 (1) Å) is significantly shorter than in FXeN(SO2F)2 (2, 200 (3) A). The Sb3FI6” anion is cis-fluorine bridged and weakly covalently bonded by means of a fluorine bridge to the XeN(SO2F)2 +cation (Xe---F = 2.457 (8) Å).
AB - Like its XeF2 precursor, the Xe-N-bonded FXeN(SO2F)2molecule exhibits fluoride ion donor properties that, in the present work, have resulted in the syntheses of adducts having the stoichiometries FXeN(SO2F)2.AsF5, FXeN(SO2F)2-3SbF5, and 2FXeN-(SO2F)2*AsF5. All compounds have been enriched to 30% with 15N and studied by 15N, 19F, and 129Xe NMR spectroscopy and Raman spectroscopy. The spectroscopic studies have shown the above stoichiometries to be consistent with the predominantly ionic formulations XeN(SO2F)2 +AsF6“, XeN(SO2F)2 +Sb3F16 -, and F[XeN(SO2F)2]2 +AsF6 -. In general, the cations are thermally less stable than their fluorine analogues, XeF+and Xe2F3 +. The crystal structure of XeN(SO2F)2 +Sb3F16~ has been obtained at -64 °C from three-dimensional X-ray data. [Bis(fluorosulfuryl)amido]xenon(II) hexadecafluorotriantimonate(V) crystallizes in the monoclinic system, space group P21/c, with four molecules in a unit cell of dimensions a = 10, 320 (2) Å, b = 10.642 (2) Å, c = 18.167 (3) Å, and β = 108, 94 (1)°. The structure was solved by the heavy-atom method and refined by least-squares and Fourier methods to a final R factor of 0.061 for 2376 observed (F > 0) reflections. The structure analysis has established the existence of discrete XeN(SO2F)2 +Sb3F16“ molecules and shows that the XeN(SO2F)2 +cation is Xe-N bonded and that the Xe-N bond (2.02 (1) Å) is significantly shorter than in FXeN(SO2F)2 (2, 200 (3) A). The Sb3FI6” anion is cis-fluorine bridged and weakly covalently bonded by means of a fluorine bridge to the XeN(SO2F)2 +cation (Xe---F = 2.457 (8) Å).
UR - http://www.scopus.com/inward/record.url?scp=0001526457&partnerID=8YFLogxK
U2 - 10.1021/ic00224a035
DO - 10.1021/ic00224a035
M3 - Journal Article
AN - SCOPUS:0001526457
SN - 0020-1669
VL - 25
SP - 563
EP - 571
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 4
ER -