Cis- and trans-binding influences in [NUO·(N2)n]+

Author:

Zhao Jing1ORCID,Chi Chao-Xian2,Meng Lu-Yan3,Jiang Xue-Lian4,Grunenberg Jörg5,Hu Han-Shi1,Zhou Ming-Fei6ORCID,Li Jun14,Schwarz W. H. Eugen17ORCID

Affiliation:

1. Key Laboratory of Organo-Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, China

2. Key Laboratory of Advanced Mass Spectrometry and Molecular Analysis of Zhejiang Province, Ningbo University, Ningbo, Zhejiang 315211, China

3. School of Chemistry, Biological and Materials Sciences, East China University of Technology, Nanchang, Jiangxi Province 330013, China

4. Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong Province 518055, China

5. Institut für Organische Chemie, TU Braunschweig, Braunschweig 38106, Germany

6. Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200438, China

7. Laboratory of Physical and Theoretical Chemistry, Siegen University, Siegen 57068, Germany

Abstract

Uranium nitride-oxide cations [NUO]+ and their complexes with equatorial N2 ligands, [NUO·(N2) n]+ ( n = 1–7), were synthesized in the gas phase. Mass-selected infrared photodissociation spectroscopy and quantum chemical calculations confirm [NUO·(N2)5]+ to be a sterically fully coordinated cation, with electronic singlet ground state of 1A1, linear [NUO]+ core, and C5v 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 N2 ligands has also been explained, highlighting the bonding characteristics and distinct features of uranium chemistry.

Publisher

AIP Publishing

Subject

Physical and Theoretical Chemistry,General Physics and Astronomy

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