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Updated: Oct 21, 2025

Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
Published on: June 8, 2022
Realization of the Zn3+ oxidation state
Hong Fang1, Huta Banjade, Deepika
1Physics Department, Virginia Commonwealth University, Richmond, VA 23284, USA. pjena@vcu.edu.
Abstract:
Due to unfilled d-shells, transition metal atoms exhibit multiple oxidation states and rich chemistry. While zinc is often classified as a transition metal, electrons in its filled 3d10 shell do not participate in chemical reactions; hence, its oxidation state is +2. Using calculations based on density functional theory, we show that the chemistry of zinc can fundamentally change when it is allowed to interact with highly stable super-electrophilic trianions, namely, BeB11(CN)123- and BeB23(CN)223-, which lie 15.85 eV and 18.49 eV lower in energy than their respective neutral states. The fact that Zn exists in +3 oxidation states while interacting with these moieties is evidenced from its large binding energies of 6.33 and 7.04 eV with BeB11(CN)123- and BeB23(CN)223-, respectively, and from a comprehensive analysis of its bonding characteristics, charge density distribution, electron localization function, molecular orbitals and energy decomposition, all showing a strong involvement of its 3d electrons in chemical bonding. The replacement of CN with BO is found to increase the zinc binding energy even further.
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