AI Article Synopsis
- The study investigates lanthanide-oxide nitrate complexes, specifically [Ln(O)(NO)], formed from trivalent lanthanide nitrates by eliminating NO.
- These complexes exhibit varying types of Ln-O bonding (oxyl and oxo) based on the accessibility of the tetravalent state of the lanthanides.
- It is discovered that praseodymium (PrO) showcases slower reactivity compared to terbium (TbO), indicating a more stable oxo bond in Pr, which is a unique finding in the context of their comparative chemical properties.
Article Abstract
We report on the reactivity of gas-phase lanthanide-oxide nitrate complexes, [Ln(O)(NO)] (denoted LnO), produced via elimination of NO from trivalent [Ln(NO)] (Ln = Ce, Pr, Nd, Sm, Tb, Dy). These complexes feature a Ln-O oxyl, a Ln═O oxo, or an intermediate Ln oxyl/oxo bond, depending on the accessibility of the tetravalent Ln state. Hydrogen atom abstraction reactivity of the LnO complexes to form unambiguously trivalent [Ln(OH)(NO)] reveals the nature of the oxide bond. The result of slower reactivity of PrO versus TbO is considered to indicate higher stability of the tetravalent praseodymium-oxo, Pr═O, versus Tb═O. This is the first report of Pr as more stable than Tb, which is discussed with respect to ionization potentials, standard electrode potentials, atomic promotion energies, and oxo bond covalency via 4f- and/or 5d-orbital participation.
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| http://dx.doi.org/10.1021/acs.inorgchem.2c00525 | DOI Listing |
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