Issue 26, 2018

An ab initio study on coinage atom-inserted cyanide/isocyanide: XMCN/XMNC (M = coinage atoms; X = halogen)

Abstract

The coinage atom-inserted cyanide/isocyanide compounds, XMCN and XMNC (X = halogens) formed by the insertion of a coinage atom into the X–C(N) bonds of XCN (or XNC), were investigated by ab initio methods. XMCN was predicted to be more stable than XMNC, which is different from the case of XUCN/XUNC reported previously. Based on the analyses on the ionization dissociation pathways, the M–C (or M–N) bond is more easily broken than the X–M bond. Moreover, the order of the M–C (or M–N) bond energy in XMCN (or XMNC) is XAuCN (XAuNC) > XCuCN (XCuNC) > XAgCN (XAgNC). The shift characters of vC–N in XMCN (or XMNC) with respect to the concerning precursor can be used to identified XMCN and XMNC experimentally. The results of charge decomposition analysis (CDA) and atoms-in-molecule (AIM) illustrate that the X–M and M–C(N) bond behaves as a coordination bond, while the C–N bond is a typical polar covalent bond. The higher thermodynamic stability of XMCN is the result of the –CN group having better coordination ability than the –NC group.

Graphical abstract: An ab initio study on coinage atom-inserted cyanide/isocyanide: XMCN/XMNC (M = coinage atoms; X = halogen)

Supplementary files

Article information

Article type
Paper
Submitted
14 Jan 2018
Accepted
09 Apr 2018
First published
18 Apr 2018
This article is Open Access
Creative Commons BY-NC license

RSC Adv., 2018,8, 14705-14712

An ab initio study on coinage atom-inserted cyanide/isocyanide: XMCN/XMNC (M = coinage atoms; X = halogen)

Z. Huang, X. Wang, J. Zhang, Y. Li and Y. Li, RSC Adv., 2018, 8, 14705 DOI: 10.1039/C8RA00397A

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements