Issue 46, 2023

Cluster size dependent coordination of formate to free manganese oxide clusters

Abstract

The interaction of free manganese oxide clusters, MnxOy+ (x = 1–9, y = 0–12), with formic acid was studied via infrared multiple-photon dissociation (IR-MPD) spectroscopy together with calculations using density functional theory (DFT). Clusters containing only one Mn atom, such as MnO2+ and MnO4+, bind formic acid as an intact molecule in both the cis- and trans-configuration. In contrast, all clusters containing two or more manganese atoms deprotonate the acid's hydroxyl group. The coordination of the resulting formate group is strongly cluster-size-dependent according to supporting DFT calculations for selected model systems. For Mn2O2+ the co-existence of two isomers with the formate bound in a bidentate bridging and chelating configurations, respectively, is found, whereas for Mn2O4+ the bidentate chelating configuration is preferred. In contrast, the bidentate bridging structure is energetically considerably more favorable for Mn4O4+. This binding motif stabilizes the 2D ring structure of the core of the Mn4O4+ cluster with respect to the 3D cubic geometry of the Mn4O4+ cluster core.

Graphical abstract: Cluster size dependent coordination of formate to free manganese oxide clusters

Article information

Article type
Paper
Submitted
22 ago 2023
Accepted
14 nov 2023
First published
14 nov 2023
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2023,25, 32166-32172

Cluster size dependent coordination of formate to free manganese oxide clusters

S. M. Lang, T. M. Bernhardt, J. M. Bakker, R. N. Barnett and U. Landman, Phys. Chem. Chem. Phys., 2023, 25, 32166 DOI: 10.1039/D3CP04035F

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements