Zhao Jing, Chi Chao-Xian, Meng Lu-Yan, Jiang Xue-Lian, Grunenberg Jörg, Hu Han-Shi, Zhou Ming-Fei, Li Jun, Schwarz W H Eugen
Key Laboratory of Organo-Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, China.
Key Laboratory of Advanced Mass Spectrometry and Molecular Analysis of Zhejiang Province, Ningbo University, Ningbo, Zhejiang 315211, China.
J Chem Phys. 2022 Aug 7;157(5):054301. doi: 10.1063/5.0098068.
Uranium nitride-oxide cations [NUO] and their complexes with equatorial N ligands, [NUO·(N)] (n = 1-7), were synthesized in the gas phase. Mass-selected infrared photodissociation spectroscopy and quantum chemical calculations confirm [NUO·(N)] to be a sterically fully coordinated cation, with electronic singlet ground state of A, linear [NUO] core, and C structure. The presence of short N-U bond distances and high stretching modes, with slightly elongated U-O bond distances and lowered stretching modes, is rationalized by attributing them to cooperative covalent and dative [ǀN≡U≡Oǀ] triple bonds. The mutual trans-interaction through flexible electronic U-5f6d7sp valence shell and the linearly increasing perturbation with increase in the number of equatorial dative N ligands has also been explained, highlighting the bonding characteristics and distinct features of uranium chemistry.
氮化铀酰阳离子[NUO]及其与赤道面N配体的配合物[NUO·(N)]（n = 1 - 7）在气相中合成。质量选择红外光解离光谱和量子化学计算证实[NUO·(N)]是一种空间上完全配位的阳离子，具有A电子单重基态、线性[NUO]核心和C结构。通过将短的N - U键距离和高伸缩模式以及稍长的U - O键距离和降低的伸缩模式归因于协同共价和配位[ǀN≡U≡Oǀ]三键，对其进行了合理解释。还解释了通过灵活的U - 5f6d7sp价电子壳层的相互反式相互作用以及随着赤道面配位N配体数量增加而线性增加的扰动，突出了铀化学的键合特征和独特特性。
