Journal article
Structural and Theoretical Assessment of Covalency in a Pu(III) Borohydride Complex
Journal of the American Chemical Society, Vol.146(38), pp.25943-25948
09/16/2024
DOI: 10.1021/jacs.4c09888
PMCID: PMC11440501
PMID: 39283691
Appears in UI Libraries Support Open Access
Abstract
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 Pu2(H3BPtBu2BH3)6, 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 M2(H3BPtBu2BH3)6 complexes generally decreases in the order M = U(III) > Pu(III) > Ln(III).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 Pu2(H3BPtBu2BH3)6, 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 M2(H3BPtBu2BH3)6 complexes generally decreases in the order M = U(III) > Pu(III) > Ln(III).
Details
- Title: Subtitle
- Structural and Theoretical Assessment of Covalency in a Pu(III) Borohydride Complex
- Creators
- Joshua C Zgrabik - University of IowaDaniel J Lussier - Los Alamos National LaboratoryRina Bhowmick - University of South DakotaNgan Nguyen - University of South DakotaPeter A Zacher - University of IowaTatyana Elkin - Los Alamos National LaboratoryAndrew J Gaunt - Los Alamos National LaboratoryGeorge S Goff - Los Alamos National LaboratoryHarris E Mason - Los Alamos National LaboratoryJesse Murillo - Los Alamos National LaboratoryBrian L Scott - Los Alamos National LaboratoryBess Vlaisavljevich - University of IowaScott R Daly - University of Iowa
- Resource Type
- Journal article
- Publication Details
- Journal of the American Chemical Society, Vol.146(38), pp.25943-25948
- DOI
- 10.1021/jacs.4c09888
- PMID
- 39283691
- PMCID
- PMC11440501
- NLM abbreviation
- J Am Chem Soc
- ISSN
- 1520-5126
- eISSN
- 1520-5126
- Publisher
- American Chemical Society
- Grant note
- Office of Advanced Cyberinfrastructure: 20220518MFR Laboratory Directed Research and Development (LDRD) program of Los Alamos National Laboratory: DE-AC52-06NA25396 U.S. DOE Office of Science, BES, Heavy Element Chemistry Program at Los Alamos National Laboratory: DE-SC0023022, DE-NA0004151 U.S. Department of Energy, Office of Science, Basic Energy Sciences, in the Heavy Element Chemistry program: OAC-1626516
Research presented in this manuscript was supported by the Laboratory Directed Research and Development (LDRD) program of Los Alamos National Laboratory under project number 20220518MFR. DJL and AJG thank the U.S. DOE Office of Science, BES, Heavy Element Chemistry Program at Los Alamos National Laboratory (DE-AC52-06NA25396) for repeat synthesis and spectroscopic characterization of the plutonium complex. RRB, NN, and BV were supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, in the Heavy Element Chemistry program (Grant no. DE-SC0023022). SRD and PAZ also thank the NNSA for support (DE-NA0004151). Computations supporting this project performed on high-performance computing systems were made possible by resources funded by NSF award OAC-1626516.
- Language
- English
- Date published
- 09/16/2024
- Academic Unit
- Chemistry
- Record Identifier
- 9984708950502771
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