Structural and Theoretical Assessment of Covalency in a Pu(III) Borohydride Complex
Despite the discovery of actinide borohydride complexes over 80 years ago, no plutonium borohydride complexes have been structurally validated using single-crystal X-ray diffraction (XRD). Here we describe Pu<sub>2</sub>(H<sub>3</sub>BP<sup><i>t</i></sup>Bu<sub>2</sub>BH<sub>3</sub>)<sub>6</sub>, the first example of a Pu(III) borohydride complex authenticated by XRD and NMR spectroscopy. Theoretical calculations (DFT, EDA, and QTAIM) and experimental comparisons of metal-boron distances suggest that metal-borohydride covalency in M<sub>2</sub>(H<sub>3</sub>BP<sup><i>t</i></sup>Bu<sub>2</sub>BH<sub>3</sub>)<sub>6</sub> complexes generally decreases in the order M = U(III) > Pu(III) > Ln(III).
Authors
- Jesse Murillo (ORCID: https://orcid.org/0000-0002-9786-6948)
- Bess Vlaisavljevich (ORCID: https://orcid.org/0000-0001-6065-0732)
- Andrew J. Gaunt (ORCID: https://orcid.org/0000-0001-9679-6020)
- Rina Bhowmick (ORCID: https://orcid.org/0000-0002-2003-3139)
- Joshua C. Zgrabik
- George S. Goff (ORCID: https://orcid.org/0000-0003-2232-8501)
- Scott R. Daly (ORCID: https://orcid.org/0000-0001-6229-0822)
- Harris E. Mason (ORCID: https://orcid.org/0000-0002-1840-0550)
- Daniel J. Lussier (ORCID: https://orcid.org/0000-0002-6715-6443)
- Tatyana Elkin (ORCID: https://orcid.org/0000-0001-8518-1987)
- Ngan Nguyen
- Brian L. Scott (ORCID: https://orcid.org/0000-0002-8528-9936)
- Peter A. Zacher (ORCID: https://orcid.org/0009-0003-9715-9340)
Institutions
- University of Iowa (US)
- Los Alamos National Laboratory (US)
- University of South Dakota (US)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2024-09-16
- DOI
- https://doi.org/10.1021/jacs.4c09888
- Citations
- 5
- Primary Topic
- Radioactive element chemistry and processing
- Type
- article
- Field-Weighted Citation Impact
- 0.79
Funders
- University of South Dakota
- National Nuclear Security Administration
- Office of Advanced Cyberinfrastructure
- Basic Energy Sciences
- Laboratory Directed Research and Development
- Los Alamos National Laboratory