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

Abstract

We present a study of the isoelectronic Pt₂Ng₂F₄ and [Au₂Ng₂F₄]²⁺ 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 [AuXe₄]²⁺, 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 [AuXe₄](Sb₂F₁₁)₂ (S. Seidel and K. Seppelt, Science, 2000, 290, 117–118). Our results indicate that improving upon [AuXe₄]²⁺, 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.