Abstract

Nitrogen has five valence electrons and can form a maximum of three shared electron-pair bonds to complete its octet, which suggests that its maximum bond order is three. With a joint anion photoelectron spectroscopy and quantum chemistry investigation, we report herein that nitrogen presents a quadruple bonding interaction with thorium in ThN. The quadruple Th≣N bond consists of two electron-sharing Th-N π bonds formed between the Th-6dxz/6dyz and N 2px/2py orbitals, one dative Th←N σ bond and one weak Th←N σ bonding interaction formed between Th-6dz2 and N 2s/2pz orbitals. The ThC molecule has also been investigated and proven to have a similar bonding pattern as ThN. Nonetheless, due to one singly occupied σ-bond, ThC is assigned a bond order of 3.5. Moreover, ThC has a longer bond length as well as a lower vibrational frequency in comparison with ThN.

Nitrogen can form a maximum of three shared electron-pair bonds to complete its octet, suggesting the maximum bond order of nitrogen is three. Here, the authors report a joint photoelectron spectroscopy and quantum chemical study, showing a quadruple bond between nitrogen and thorium in thorium nitride.

Details

Title
The unusual quadruple bonding of nitrogen in ThN
Author
Fei, Zejie 1 ; Wang, Jia-Qi 2 ; Tang, Rulin 3 ; Lu, Yuzhu 3 ; Han, Changcai 1 ; Wang, Yongtian 1 ; Hong, Jing 4 ; Dong, Changwu 1 ; Hu, Han-Shi 5   VIAFID ORCID Logo  ; Xiong, Xiao-Gen 6   VIAFID ORCID Logo  ; Ning, Chuangang 3 ; Liu, Hongtao 1 ; Li, Jun 5   VIAFID ORCID Logo 

1  Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Key Laboratory of Interfacial Physics and Technology, Shanghai, China (GRID:grid.450275.1) (ISNI:0000 0000 9989 3072) 
2  Tsinghua University, Department of Chemistry, Beijing, China (GRID:grid.12527.33) (ISNI:0000 0001 0662 3178); Beijing Forestry University, College of Science, Beijing, China (GRID:grid.66741.32) (ISNI:0000 0001 1456 856X) 
3  Collaborative Innovation Center of Quantum Matter, Tsinghua University, Department of Physics, State Key Laboratory of Low Dimensional Quantum Physics, Beijing, China (GRID:grid.495569.2) 
4  Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Key Laboratory of Interfacial Physics and Technology, Shanghai, China (GRID:grid.450275.1) (ISNI:0000 0000 9989 3072); University of Chinese Academy of Sciences, Beijing, China (GRID:grid.410726.6) (ISNI:0000 0004 1797 8419) 
5  Tsinghua University, Department of Chemistry, Beijing, China (GRID:grid.12527.33) (ISNI:0000 0001 0662 3178) 
6  Sun Yat-sen University, Sino-French Institute of Nuclear Engineering and Technology, Zhuhai, China (GRID:grid.12981.33) (ISNI:0000 0001 2360 039X) 
Pages
7677
Publication year
2023
Publication date
2023
Publisher
Nature Publishing Group
e-ISSN
20411723
Source type
Scholarly Journal
Language of publication
English
DOI
https://doi.org/10.1038/s41467-023-43208-z
ProQuest document ID
2892805154
Copyright
© The Author(s) 2023. corrected publication 2023. This work is published under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.