Preprint
Praseodymium in the Formal +5 Oxidation State
ChemRxiv
09/04/2024
DOI: 10.26434/chemrxiv-2024-cb3zj
Abstract
The pentavalent oxidation state of praseodymium – a long-sought connection between lanthanide, early-transition, and actinide metal redox chemistries – has only been identified in gas-phase or matrix isolation environments. We report the low-temperature characterization of a molecular praseodymium complex in the formal +5 oxidation state, [Pr5+(NP(tBu3)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 Boggiano - Georgia Institute of TechnologyChad Studvick - University of AkronSabyasachi Roy Chowdhury - University of Iowa, ChemistryJulie Niklas - Georgia Institute of TechnologyHaruko Tateyama - Georgia Institute of TechnologyHongwei Wu - Georgia Institute of TechnologyJohannes Leisen - Georgia Institute of TechnologyFlorian Kleemiss - RWTH Aachen UniversityBess Vlaisavljevich - University of Iowa, ChemistryIvan Popov - Washington State UniversityHenry La Pierre - Pacific Northwest National Laboratory
- Resource Type
- Preprint
- Publication Details
- ChemRxiv
- DOI
- 10.26434/chemrxiv-2024-cb3zj
- ISSN
- 2573-2293
- Number of pages
- 14 pages
- Language
- English
- Date posted
- 09/04/2024
- Academic Unit
- Chemistry
- Record Identifier
- 9984800306202771
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