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A tetranuclear nickel cluster isolated in multiple high-valent states
Samuel I Jacob1, Iskander Douair, Guang Wu
1Department of Chemistry and Biochemistry, University of California, Santa Barbara, CA 93106, USA. menard@chem.ucsb.edu.
Chemical Communications (Cambridge, England)
|April 16, 2020
Summary
Researchers chemically oxidized a neutral nickel cluster ([Ni4]) to create high-valent species. This study successfully isolated the first tetranuclear all-nickel(iii) cluster, [Ni4]4+, through sequential oxidation.
Area of Science:
- Inorganic Chemistry
- Materials Science
- Electrochemistry
Background:
- Nickel clusters are crucial in catalysis and materials science.
- Understanding high-valent metal clusters is key to developing new chemical transformations.
- The synthesis and characterization of polynuclear high-valent metal complexes remain challenging.
Purpose of the Study:
- To investigate the electrochemical oxidation of an all Ni(II) tetranuclear nickel cluster.
- To isolate and characterize high-valent nickel cluster species.
- To determine the electronic structure and oxidation sites within the cluster.
Main Methods:
- Chemical oxidation of a neutral Ni4 cluster.
- Electrochemical analysis (cyclic voltammetry) to determine oxidation potentials.
- Spectroscopic techniques (e.g., UV-Vis, EPR) for electronic structure determination.
- X-ray crystallography for structural elucidation.
- Magnetometry for magnetic property analysis.
- Computational methods (e.g., DFT) for electronic structure calculations.
Main Results:
- The neutral Ni4 cluster undergoes three reversible sequential oxidations at 0.248 V (1e-), 0.678 V (1e-), and 0.991 V (2e-).
- Oxidation primarily occurs at the Ni centers, leading to mono-, di-, and tetra-oxidized species ([Ni4]+, [Ni4]2+, [Ni4]4+).
- The first tetranuclear all-Ni(III) cluster, [Ni4]4+, was successfully isolated and characterized.
Conclusions:
- The study demonstrates the feasibility of accessing high-valent nickel clusters through controlled chemical oxidation.
- The isolation of the all-Ni(III) cluster provides a new platform for exploring Ni(III) chemistry.
- This work expands the known range of polynuclear high-valent metal complexes and their electronic properties.
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