Cyanide-isocyanide isomerization: stability and bonding in noble gas inserted metal cyanides (metal = Cu, Ag, Au)

The internal isomerization, MNC ↔ MCN (M = Cu, Ag, Au), is investigated through quantum chemical computations. CuNC and AgNC are shown to be neither thermochemically nor kinetically stable against transformation to MCN. The free energy barrier (ΔG^‡) for AuNC is somewhat considerable (7.1 kcal mol^-1), indicating its viability, particularly at low temperature. Further, the Ng inserted analogues, MNgCN (M = Cu, Ag, Au; Ng = Xe, Rn) turn out to be thermochemically stable with respect to all possible dissociation channels but for two two-body dissociation channels, viz., MNgCN → Ng + MCN and MNgCN → Ng + MNC, which are connected to the internal isomerization processes, MNgCN → NgMCN and MNgCN → NgMNC, respectively. However, they are kinetically protected by substantial ΔG^‡ values (11.8-15.4 kcal mol^-1 for Cu, 9.8-13.6 kcal mol^-1 for Ag, and 19.7-24.7 kcal mol^-1 for Au). The pathways for such internal conversion are explored in detail. A thorough inspection of the bonding situation of the studied molecules, employing natural bond order, electron density, adaptive natural density partitioning, and energy decomposition analyses indicates that the M-Ng bonds in MNgCN and Ng-C bonds in AuNgCN can be represented as an electron-shared covalent bond. For the other Ng-C bonds, although an ionic description is better suited, the degree of covalent character is also substantial therein.