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

Jake M Seymour¹, Ekaterina Gousseva¹, Lewis G Parker¹

¹Department of Chemistry, University of Reading, Reading RG6 6DX, U.K.

The Journal of Physical Chemistry Letters

|March 10, 2025

Summary

Liquid-phase d¹⁰s² post-transition metal anions exhibit dual Lewis base behavior, interacting via metal or ligand depending on the electron acceptor. Metal identity primarily controls basicity, with ligands offering fine-tuning for catalysis.

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Area of Science:

Inorganic chemistry
Computational chemistry
Catalysis

Background:

d¹⁰s² post-transition metal anions are utilized in catalysis and material science.
Their electronic structure and reactivity relationship is not well understood.

Purpose of the Study:

To investigate the electronic structure and Lewis basicity of liquid-phase d¹⁰s² post-transition metal anions.
To elucidate how electronic structure influences reactivity in catalytic applications.

Main Methods:

X-ray photoelectron spectroscopy (XPS) for electronic structure analysis.
Ab initio calculations for theoretical modeling and reactivity prediction.

Main Results:

Demonstrated dual-mode Lewis base behavior of these anions.
Identified metal center and ligand as key interaction points, dependent on the Lewis acid.
Established metal identity as the primary determinant of Lewis basicity, with ligands for fine-tuning.

Conclusions:

Liquid-phase d¹⁰s² post-transition metal anions possess tunable electronic structures.
Understanding their dual Lewis base nature enables precise molecular design for enhanced catalytic systems.