Super-electrophiles of tri- and tetra-anions stabilized by selected terminal groups and their role in binding noble gas atoms

Abstract

Stabilization of multiply-charged atomic clusters in the gas phase has been a topic of great interest not only because of their potential applications as weakly-coordinating anions, but also for their...

Noble Gas Anions: An Overview of Strategies and Bonding Motifs

“…Overall, the peculiar ability of the [B 12 X 11 ] − to form complexes with the Ng atoms results from various concurring factors, [94] namely the strong electrophilicity of the B atom, the kinetically‐favored approach to the B atom of an apolar nucleophile, the structural stability of the cluster preventing intramolecular rearrangements of the [B 12 X 11 (Ng)] − , the steric protection by the cage against further substitution of the fixed Ng, and the occurrence in the formed complex of favorable electrostatic and dispersion interactions which add to the inductive (donor‐acceptors) stabilizing forces. With these ingredients in mind, various theoretical groups explored the conceivable existence of systems analogous to the [B 12 X 11 ] − that are still able to fix the Ng atoms [98–102] . It first emerged that the family of the [B 12 X 11 ] − is probably larger than that sampled in the experiments, clusters such as [B 12 (BO) 11 ] − and [B 12 (OBO) 11 ] −[98,99] being predicted to be in principle capable to fix the Ng atoms with binding energies comparable with those of the [B 12 Cl 11 ] − and [B 12 (CN) 11 ] − .…”

BH4Ng+ (Ar−Rn): Viable Compounds with a B−Ng Covalent Bond

“…The results complement the BOMD calculations, showing that the formation of both bonds takes place without any energy barrier. Finally, the NgÀ B bonds distances are compared with those of other similar species reported in the literature,the literature, [11][12][13][14][38][39][40][41][46][47][48][49][50] where the covalent character of this interaction has been highlighted (see Table S1). For example, NgÀ B bond distances in the NgBH4 + series tend to be longer for He and Ne but equalise for the ArÀ Rn series when compared to other reported systems.…”

In silico capture of noble gas atoms with a light atom molecule

“…[22][23][24][25][26][27] Recent studies showed that heavier Ng atoms can be attached to super-electrophiles like [B 12 (CN) 11 ] À . [28][29][30][31][32][33][34] A recent DFT study investigated the binding towards MCp (M = Be-Ba) half-sandwich complexes. 35 No bonding interaction was ever observed involving a He atom, disregarding the heavily debated and still hypothetical He@adamantane case.…”