Liquid-phase ds post-transition metal anions, such as [SnCl], 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 calculations, we demonstrate that liquid-phase ds 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 ds post-transition metal anion electronic structure, which will enable better molecular-level design of catalytic systems.
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