Observations regarding the synthesis and redox chemistry of heterobimetallic uranyl complexes containing Group 10 metals

Emily R. Mikeska; Natalie M. Lind; Alexander C. Ervin; Celine Khalife; Joseph P. Karnes; James D. Blakemore

doi:10.1515/ract-2023-0237

Abstract

Literature reports have demonstrated that Schiff-base-type ligands can serve as robust platforms for the synthesis of heterobimetallic complexes containing transition metals and the uranyl dication (UO₂ ²⁺). However, efforts have not advanced to include either synthesis of complexes containing second- or third-row transition metals or measurement of the redox properties of the corresponding heterobimetallic complexes, despite the significance of actinide redox in studies of nuclear fuel reprocessing and separations. Here, metalloligands denoted [Ni], [Pd], and [Pt] that contain the corresponding Group 10 metals have been prepared and a synthetic strategy to access species incorporating the uranyl ion (UO₂ ²⁺) has been explored, toward the goal of understanding how the secondary metals could tune uranium-centered redox chemistry. The synthesis and redox characterization of the bimetallic complex [Ni,UO₂] was achieved, and factors that appear to govern extension of the chosen synthetic strategy to complexes with Pd and Pt are reported here. Infrared and solid-state structural data from X-ray diffraction analysis of the metalloligands [Pd] and [Pt] show that the metal centers in these complexes adopt the expected square planar geometries, while the structure of the bimetallic [Ni,UO₂] reveals that the uranyl moiety influences the coordination environment of Ni(II), including inducement of a puckering of the ligand backbone of the complex in which the phenyl rings fold around the nickel-containing core in an umbrella-shaped fashion. Cyclic voltammetric data collected on the heterobimetallic complexes of both Ni(II) and Pd(II) provide evidence for uranium-centered redox cycling, as well as for the accessibility of other reductions that could be associated with Ni(II) or the organic ligand backbone. Taken together, these results highlight the unique redox behaviors that can be observed in multimetallic systems and design concepts that could be useful for accessing tunable multimetallic complexes containing the uranyl dication.

Keywords: crystallography; electrochemistry; protonolysis; uranium; nickel

Corresponding author: James D. Blakemore, Department of Chemistry, University of Kansas, 1567 Irving Hill Road, Lawrence 66045, KS, USA, E-mail: blakemore@ku.edu.

Acknowledgments

The authors thank Dr. William Brennessel (CENTC Elemental Analysis Facility, University of Rochester funded by NSF CHE-0650456) for assistance with elemental analysis.

Research ethics: Not applicable.
Author contributions: The authors have have accepted responsibility for the entire content of this manuscript and approved its submission.
Competing interests: The authors state no conflict of interest.
Research funding: This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences through the Early Career Research Program (DE-SC0019169). N.M.L. was supported by NSF REU Program in Chemistry at the University of Kansas (CHE-1950293), and E.R.M., A.C.E., and J.P.K. were supported by a U.S. National Science Foundation Research Traineeship (NRT) at the University of Kansas (DGE-1922649).
Data availability: The raw data can be obtained on request from the corresponding author.

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Supplementary Material

This article contains supplementary material (https://doi.org/10.1515/dx-2023-0237).

Received: 2023-10-04

Accepted: 2024-01-19

Published Online: 2024-02-09

Published in Print: 2024-03-25

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