DOE OSTI · 2863918
Praseodymium in the formal +5 oxidation state
Abstract
Praseodymium in the +5 oxidation state is a long-sought connection between lanthanide, early-transition and actinide metal redox chemistries. Unique among the lanthanide series, evidence for molecular pentavalent praseodymium species has been observed in the gas phase and noble gas matrix isolation conditions. Here we report the low-temperature synthesis and characterization of a molecular praseodymium complex in the formal +5 oxidation state, [Pr 5+ (NP t Bu 3 ) 4 ][X − ] (where t Bu = tert -butyl and X − = tetrakis(pentafluorophenyl)borate or hexafluorophosphate). Single-crystal X-ray diffraction, solution-state spectroscopic, solution magnetometric, density functional theory and multireference wavefunction-based methods indicate a highly multiconfigurational singlet ground state. Finally, an inverted ligand field drives this unique electronic structure, which establishes a critical link in understanding the bonding of high-valent metal complexes across the periodic table.
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Boggiano, Andrew C. [Georgia Institute of Technology, Atlanta, GA (United States)] (ORCID:000000025444485X), Studvick, Chad M. [Univ. of Akron, OH (United States)] (ORCID:000000024249776X), Roy Chowdhury, Sabyasachi [Univ. of South Dakota, Vermillion, SD (United States); Univ. of Iowa, Iowa City, IA (United States)] (ORCID:0000000190008476), Niklas, Julie E. [Georgia Institute of Technology, Atlanta, GA (United States)], Tateyama, Haruko [Georgia Institute of Technology, Atlanta, GA (United States)] (ORCID:0000000323829420), Wu, Hongwei [Georgia Institute of Technology, Atlanta, GA (United States)] (ORCID:0000000286873843), Leisen, Johannes E. [Georgia Institute of Technology, Atlanta, GA (United States)] (ORCID:000000030474670X), Kleemiss, Florian [RWTH Aachen Univ. (Germany)] (ORCID:0000000236311535), Vlaisavljevich, Bess [Univ. of South Dakota, Vermillion, SD (United States); Univ. of Iowa, Iowa City, IA (United States)] (ORCID:0000000160650732), Popov, Ivan A. [Washington State Univ., Pullman, WA (United States)] (ORCID:0000000326633685), La Pierre, Henry S. [Georgia Institute of Technology, Atlanta, GA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)] (ORCID:0000000208950655). 2025-04-07. Praseodymium in the formal +5 oxidation state. https://doi.org/10.1038/s41557-025-01797-w
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