Bond Dissociation Energy and Lewis Acidity of the Xenon Fluoride Cation

Abstract

This study focuses upon the Lewis acid reactivity of XeF(+) with various bases in the gas phase and the determination of the bond dissociation energy of XeF(+). The bond dissociation energy of XeF(+) has been measured by using energy-resolved collision-induced dissociation with neon, argon, and xenon target gases. Experiments with neon target yield a 298 K bond dissociation enthalpy of 2.81 +/- 0.09 eV, and those with argon target give a similar value at 2.83 +/- 0.12 eV. When using a xenon target, a significantly lower value of 1.95 +/- 0.16 eV was observed, which corresponds closely with previous measurements and theoretical predictions. It is proposed that the lighter target gases give inefficient excitation of the XeF(+) vibration leading to dissociation at energies higher than the BDE. Novel xenon-base adducts have been prepared in a flowing afterglow mass spectrometer by termolecular addition to XeF(+) and by reaction of base with XeF(+)(H(2)O). New species have been characterized qualitatively by CID, and it is found that the products formed reflect the relative ionization energies of the fragments. Among the new xenon-containing species that have been prepared are the first examples of xenon carbonyls.

The essential role of charge-shift bonding in hypervalent prototype XeF2

“…They found an atomization energy of 2.61 eV (60.26 kcal mol 21 ), close to experimental D 0 values 16,32,33 . They also computed a bonding energy D e of 1.81 eV (41.74 kcal mol 21 ) for XeF þ , again close to the experimental value of 1.95+0.16 eV obtained from collision-induced dissociation studies 34 . D e values can be obtained from D 0 values by adding a zero point energy of 2.16 kcal mol 21 for XeF 2 and 0.92 kcal mol 21 for XeF þ (ref.…”

Xenon–Nitrogen Chemistry: Gas‐Phase Generation and Theoretical Investigation of the Xenon–Difluoronitrenium Ion F2NXe+

“…Comparison of F 2 N À Xe + with other Xe À N cations: The only xenon-nitrogen cations observed so far in the gas phase are the simplest, XeN + and XeN 2 + . [54,55] Other molecular species such as XeF + (N 2 O) [56] and Xe + (CH 3 CN) [57] have been as well reported, but their connectivities are still not ascertained. F 2 NÀXe + is indeed the first gaseous congener of the xenon-nitrenium cations (FO 2 S) 2 NXe + , [19,25] F 5 SN(H)Xe + , [33] and F 5 TeN(H)Xe + [30] observed in the condensed phase as AsF 6 À or Sb 3 F 16 À salts.…”

Direct writing of lateral fluorographene nanopatterns with tunable bandgaps and its application in new generation of moiré superlattice

“…For the fluorographene synthesis, graphene was placed under the focused electron beam irradiation [19][20][21] and simultaneously, a flux of XeF2 molecules was injected through a gas injection system. Since the electrons in the initial beam is well above the critical energy to dissociate XeF2 22,23 , the decomposition of the XeF2 molecules was induced, leading to the formation of local F radicals and finally resulting in the graphene fluorination. Here, two types of graphene samples were used: free-standing graphene (FG) on transmission electron microscopy (TEM) grid and supported graphene (SG) on SiO2 substrate ( Fig.…”