Jump to main content
Jump to site search

Issue 27, 2018
Previous Article Next Article

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

Author affiliations

Abstract

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.

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

Back to tab navigation

Supplementary files

Publication details

The article was received on 04 May 2018, accepted on 06 Jun 2018 and first published on 07 Jun 2018


Article type: Paper
DOI: 10.1039/C8CP02837K
Citation: Phys. Chem. Chem. Phys., 2018,20, 18491-18502
  •   Request permissions

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

    G. Jana, S. Pan, E. Osorio, L. Zhao, G. Merino and P. K. Chattaraj, Phys. Chem. Chem. Phys., 2018, 20, 18491
    DOI: 10.1039/C8CP02837K

Search articles by author

Spotlight

Advertisements