Shafi Ziad, Gibson John K
Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Department of Chemistry, University of California, Berkeley, California 94720, United States.
Inorg Chem. 2022 May 9;61(18):7075-7087. doi: 10.1021/acs.inorgchem.2c00525. Epub 2022 Apr 27.
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.
我们报道了通过从三价[Ln(NO)]（Ln = Ce、Pr、Nd、Sm、Tb、Dy）中消除NO生成的气相镧系元素氧化物硝酸盐配合物[Ln(O)(NO)]（表示为LnO）的反应活性。这些配合物具有Ln-O氧基、Ln═O氧代或中间的Ln氧基/氧代键，这取决于四价Ln态的可及性。LnO配合物夺取氢原子形成明确的三价[Ln(OH)(NO)]的反应活性揭示了氧化物键的性质。PrO与TbO反应较慢的结果被认为表明四价镨-氧代Pr═O比Tb═O具有更高的稳定性。这是首次报道Pr比Tb更稳定，本文通过4f和/或5d轨道参与，从电离势、标准电极电位、原子激发能和氧代键共价性方面对此进行了讨论。
