Exotic species with explicit noble metal–noble gas–noble metal linkages

Abstract

We present a study of the isoelectronic PtNgF and [AuNgF] species with noble gas atoms (Ng = Kr, Xe, Rn) acting as links bridging the two noble metal atoms. The stability of the species is investigated using several thermodynamic, kinetic and reactivity indicators. The results are compared against [AuXe], which is thermodynamically unstable in the gas phase but is stabilized in the solid state to the point that it has been experimentally detected as [AuXe](SbF) (S. Seidel and K. Seppelt, Science, 2000, 290, 117-118). Our results indicate that improving upon [AuXe], these exotic combinations between the a priori non-reactive noble metals and noble gases lead to metastable species, and, therefore, they have the possibility of existing in the solid state under adequate conditions. Our calculations include accurate energies and geometries at both the CCSD/SDDALL and MP2/SDDALL levels. We offer a detailed description of the nature of the bonding interactions using orbital and density-based analyses. The computational evidence suggests partially covalent and ionic interactions as the stabilization factors.

Noble‐Noble Strong Union: Gold at Its Best to Make a Bond with a Noble Gas Atom

“…[78] Most of them are turned out to be viable candidates for experimental realization. In the most recent study related to this topic, Moreno et al [79] presented the electronic structures of D 2h symmetric Pt 2 Ng 2 F 4 and isoelectronic [Au 2 Ng 2 F 4 ] 2 + (Ng=KrÀ Rn). Interestingly, in both the systems Ng acts as a bridging ligand.…”

On the stability and chemical bond of noble gas halide cations NgX+ (Ng = He – Rn; X = F – I)

“…Subsequently, on a laboratory scale, a variety of compounds possessing Ng‐Halogen, [ 2,11–14 ] ‐oxygen, [ 15 ] ‐sulfur, [ 16 ] ‐nitrogen, [ 17–21 ] among others, [ 22,23 ] bonds have been obtained at extreme conditions, and theoretically studied through high‐level calculations. [ 24–31 ] Those findings were even more surprising when it was realized that these compounds can form covalent bonds with other atoms, going contrary to what has been believed about the noble gas behavior. Recently, interest has grown in the study of Ng‐compounds because they were found in the interstellar medium.…”

Microsolvation of small cations and anions

“…However, care must be exercised as physical and chemical processes are not exclusive domains of low lying minima, which is especially true for weakly interacting systems. Several well‐known counterexamples are immediately available: (1) active sites in proteins and enzymes remain active even if structural variations in non‐active regions lead to high energy configurations, (2) there are documented cases of theoretically predicted high energy minima of pure water clusters that were (after prediction) experimentally located in supramolecular environments, (3) even metastable species can be found as part of larger molecular arrangements in solids . A key point here is that room and laboratory conditions (temperature ≈ 300 K, pressure ≈ 1 atm) are often extreme when compared to average conditions in the universe (≈2‐3 K and near vacuum), thus, according to Boltzmann distributions, high energy microstates have high probabilities of occurrence.…”