Quantum Chemical Calculations on Novel Molecules from Xenon Insertion into Hydrocarbons

Abstract

Ab initio calculations have been performed on novel compounds that may greatly expand the scope of rare gas chemistry. These molecules are insertion compounds of xenon into unsaturated hydrocarbons, including acetylene, benzene, and phenol. We present computational evidence that molecules such as H−Xe−C2H, H−Xe−C6H5, and H−Xe−OC6H5 exist. Computational results suggest also the existence of a series of xenon-insertion compounds for larger hydrocarbons of these types. The predictions are not restricted to molecules with only one xenon atom inserted in them but molecules such as H−Xe−C2−Xe−H and H−Xe−C2−Xe−C2−Xe−H are computationally stable as well. This suggests the existence of linear polymers H−(Xe−C2) n −Xe−H for arbitrary large n. All predicted xenon-insertion molecules form a new class of possible precursors and intermediates for synthetic organic and organoelement chemistry.

Destabilization of noble-gas hydrides by a water environment: calculations for HXeOH@(H2O)n, HXeOXeH@(H2O)n, HXeBr@(H2O)n, HXeCCH@(H2O)n

“…The instability of HNgY in water is demonstrated for four experimentally known compounds: HXeBr, 1 HXeCCH, [17][18][19] HXeOH 20 and HXeOXeH. 21 A detailed analysis for the destabilization mechanism and comparison to experimental results are given for the water based HXeOH and HXeOXeH molecules.…”

On theoretical predictions of noble-gas hydrides

“…In some cases ͑H 2 O, HF, and H 2 C 2 ͒, the agreement with the experimental data is acceptable. However, the relative success is not general, and the computational H-C bond energy of H 2 C 2n artificially increases quickly with n, [11][12][13] and the computational error exceeds 2 eV for H 2 C 6 . The increase of the electron correlation level and basis set representation in a balanced manner can improve the computed energy estimates, as it was shown for HF; 4 however, such extensive CCSD͑T͒ calculations are less tempting for large H 2 C 2n -type systems.…”

Linear and nonlinear optical properties of some organoxenon derivatives

“…1 He explained this by invoking the reduced stability of their outer electrons, due to the strong screening of the inner electrons. Although predictions for stable noble gas derivatives can be found, since at least 1902, 2 the first Xe derivative, XePtF 6 , was not reported until 1962 by Bartlett, 3 proving thus wrong the widely held opinion that the noble gases are inert. Bartlett's discovery was only the beginning for a large number of Xe derivatives, which have been reported since then.…”

“…5͔͒, their cations ͑e.g., ͓XeF͔ + ͒, the organoxenonium salts 4,6 as well as the preparation and characterization of hydrides HXeY, where Y denotes an electronegative group. 7 The first stable derivative, with a Xe-C bond, has been reported by Frohn and Jakobs in 1989.…”

“…The first prediction for a fluorine-free alkynylxenon compound was reported by Lundell et al, 6 who discussed the stability and reported the spectroscopic properties of HXeC 2 H, HXeC 2 XeH, and some other organoxenon derivatives. Khriachtchev et al 9 …”