Issue 87, 2016, Issue in Progress

Computational insights into CH3MX (M = Cu, Ag and Au; X = H, F, Cl, Br and I)

Abstract

The C–X bond activation products, CH3MX (M = Cu, Ag and Au; X = H, F, Cl, Br and I) formed by the insertion of coinage metal atoms into C–X bonds of methane and halomethanes, were investigated by density functional theory (DFT). Equilibrium geometries, harmonic vibrational frequencies, and energies were calculated. Bader's atoms-in-molecule (AIM), natural population charge (NPA) and fuzzy bond orders (FBO) calculations were performed to investigate the bonding interactions in CH3MX. As X varies from F to I, the thermodynamic stability of CH3MX with respect to CH3X + M increases, and the order of the thermodynamic stability for different coinage metals is CH3CuX > CH3AuX > CH3AgX. Although the CH3MX (M = Cu, Ag and Au; X = Cl, Br and I) were predicted to be more stable thermodynamically than the others (e.g. CH3MH and CH3MF) observed in matrix isolation experiments, they have not been identified experimentally yet, and one of the probably key reasons is that their vibrational fingerprints (νC–M and νM–X) are so low that they are beyond the detection limit of an infrared spectrometer. AIM analyses show that both C–M and M–X bonds in CH3MX exhibit mainly closed-shell interaction character, and partial covalent character contributes to them. The BCP of M–H bond just locates at the boundary between the charge concentration region and the charge depletion region, which lead to the covalent character of M–H bond being overestimated by the AIM topological parameters.

Graphical abstract: Computational insights into CH3MX (M = Cu, Ag and Au; X = H, F, Cl, Br and I)

Supplementary files

Article information

Article type
Paper
Submitted
15 Jul 2016
Accepted
31 Aug 2016
First published
31 Aug 2016

RSC Adv., 2016,6, 84016-84024

Computational insights into CH3MX (M = Cu, Ag and Au; X = H, F, Cl, Br and I)

Z. Huang, Y. Yuan, L. Sun, X. Wang and Y. Li, RSC Adv., 2016, 6, 84016 DOI: 10.1039/C6RA18033G

To request permission to reproduce material from this article, 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 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