d10s2 Post-Transition Metal Anions: Identifying and Analyzing Their Dual-Mode Lewis Basicity

Seymour, Jake M.; Gousseva, Ekaterina; Parker, Lewis G.; Towers Tompkins, Frances K.; Fogarty, Richard M.; Frankemoelle, Lennart; Rowe, Rebecca; Clarke, Coby J.; Duncan, David A.; Palgrave, Robert G.; Bennett, Roger A.; Hunt, Patricia A.; Lovelock, Kevin R. J.

Abstract

Liquid-phase d10s2 post-transition metal anions, such as [SnCl3]−, appear in a range of applications with a focus on catalysis and material preparation. However, little is known about their electronic structure and how it relates to reactivity. Using X-ray photoelectron spectroscopy and ab initio calculations, we demonstrate that liquid-phase d10s2 post-transition metal anions can act as dual-mode Lewis bases, interacting through the metal center and/or the ligands, with the interaction mode depending on the identity of the Lewis acid/electron acceptor. The Lewis basicity of the metal donor atom is controlled mainly by the metal identity; the ligand can be used for fine-tuning. Changing the metal center has a strong effect on the ligand basicity. These findings provide insight into d10s2 post-transition metal anion electronic structure, which will enable better molecular-level design of catalytic systems.

Citation

Seymour, J. M., Gousseva, E., Parker, L. G., Towers Tompkins, F. K., Fogarty, R. M., Frankemoelle, L., Rowe, R., Clarke, C. J., Duncan, D. A., Palgrave, R. G., Bennett, R. A., Hunt, P. A., & Lovelock, K. R. J. (in press). d10s2 Post-Transition Metal Anions: Identifying and Analyzing Their Dual-Mode Lewis Basicity. Journal of Physical Chemistry Letters, 16(11), 2831-2836. https://doi.org/10.1021/acs.jpclett.4c03649

• Journal Article Type: Article
• Acceptance Date: Jan 30, 2025
• Online Publication Date: Mar 10, 2025
• Deposit Date: Apr 17, 2025
• Publicly Available Date: Apr 17, 2025
• Journal: The Journal of Physical Chemistry Letters
• Electronic ISSN: 1948-7185
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 16
• Issue: 11
• Pages: 2831-2836
• DOI: https://doi.org/10.1021/acs.jpclett.4c03649
• Public URL: https://nottingham-repository.worktribe.com/output/46582062
• Publisher URL: https://pubs.acs.org/doi/full/10.1021/acs.jpclett.4c03649