Inorganic Chemistry, Vol.45, No.19, 7856-7863, 2006
Gas-phase reactions of atomic lanthanide cations with sulfur hexafluoride: Periodicity in reactivity
Room-temperature reactions of sulfur hexafluoride (SF6) have been surveyed systematically with atomic lanthanide cations (Ln(+), excluding Pm+) in the gas phase, using an inductively coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometer. Rate coefficients and product distributions were measured in helium at a pressure of 0.35 Torr and temperature of 295 K. All the Ln(+) cations were observed to react efficiently (k/k(c) > 0.24) and predominantly by single and multiple F atom and fluoride abstraction to produce both LnF(n)(+) and SFn+(where n = 1, 2, 3). The observed periodic trend in reaction efficiency along the lanthanide row matches the periodic trend in the electron-promotion energy of the Ln(+) cation. A remarkable Arrhenius-like correlation is observed for the dependence of reactivity on promotion energy: the early and late lanthanide cations exhibit effective temperatures of 45 500 and 14 000 K, respectively. SFn+ product ions are observed to be unreactive with SF6, whereas up to two molecules of SF6 have been observed to add to LnF(n)(+) product ions under the experimental operating conditions of the ICP/SIFT tandem mass spectrometer.