Journal article
Praseodymium in the formal +5 oxidation state
Nature chemistry, Vol.17(7), pp.1005-1010
07/2025
DOI: 10.1038/s41557-025-01797-w
PMID: 40195436
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, [Pr5+(NPtBu3)4][X−] (where tBu = 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. 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.
Details
- Title: Subtitle
- Praseodymium in the formal +5 oxidation state
- Creators
- Andrew C Boggiano - Georgia Institute of TechnologyChad M Studvick - University of AkronSabyasachi Roy Chowdhury - University of IowaJulie E Niklas - Georgia Institute of TechnologyHaruko Tateyama - Georgia Institute of TechnologyHongwei Wu - Georgia Institute of TechnologyJohannes E Leisen - Georgia Institute of TechnologyFlorian Kleemiss - RWTH Aachen UniversityBess Vlaisavljevich - Department of Chemistry, The University of Iowa, Iowa City, IA, USA. bess-vlaisavljevich@uiowa.eduIvan A Popov - Washington State UniversityHenry S La Pierre - Pacific Northwest National Laboratory
- Resource Type
- Journal article
- Publication Details
- Nature chemistry, Vol.17(7), pp.1005-1010
- DOI
- 10.1038/s41557-025-01797-w
- PMID
- 40195436
- NLM abbreviation
- Nat Chem
- ISSN
- 1755-4330
- eISSN
- 1755-4349
- Publisher
- NATURE PORTFOLIO; BERLIN
- Grant note
- DESC0023022 / U.S. Department of Energy (DOE) OAC1626516 / National Science Foundation (NSF)
- Language
- English
- Electronic publication date
- 04/07/2025
- Date published
- 07/2025
- Academic Unit
- Chemistry
- Record Identifier
- 9984808283702771
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