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Cyanide-Isocyanide Isomerization: Stability and Bonding in Noble Gas Inserted Metal Cyanides (Metal = Cu, Ag, Au)

Abstract

The internal isomerization, MNC ↔ MCN (M = Cu, Ag, Au), is investigated through quantum chemical calculations. 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), 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 for Cu, 9.8-13.6 kcal/mol for Ag, and 19.7-24.7 kcal/mol for Au). The possible pathways for such internal conversion are explored in detail. A thorough inspection in 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.

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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, Accepted Manuscript
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    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, Accepted Manuscript , DOI: 10.1039/C8CP02837K

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