10.1021/ic501006p.s001
Qun-Yan Wu
Qun-Yan
Wu
Cong-Zhi Wang
Cong-Zhi
Wang
Jian-Hui Lan
Jian-Hui
Lan
Cheng-Liang Xiao
Cheng-Liang
Xiao
Xiang-Ke Wang
Xiang-Ke
Wang
Yu-Liang Zhao
Yu-Liang
Zhao
Zhi-Fang Chai
Zhi-Fang
Chai
Wei-Qun Shi
Wei-Qun
Shi
Theoretical Investigation on Multiple Bonds in Terminal
Actinide Nitride Complexes
American Chemical Society
2014
actinide contraction
electron density
NBO analysis
structure changes
bond length
topological analysis
Mayer bond order
actinide series
CH
DFT
5 f
Theoretical Investigation
ground state
actinide compounds
Terminal Actinide Nitride ComplexesA series
Multiple Bonds
bond strength
2014-09-15 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Theoretical_Investigation_on_Multiple_Bonds_in_Terminal_Actinide_Nitride_Complexes/2254945
A series
of actinide (An) species of L-An-N compounds [An = Pa–Pu,
L = [N(CH<sub>2</sub>CH<sub>2</sub>NSiPr<sup>i</sup><sub>3</sub>)<sub>3</sub>]<sup>3–</sup>, Pr<sup>i</sup> = CH(CH<sub>3</sub>)<sub>2</sub>] have been investigated using scalar relativistic density
functional theory (DFT) without considering spin–orbit coupling
effects. The ground state geometric and electronic structures and
natural bond orbital (NBO) analysis of actinide compounds were studied
systematically in neutral and anionic forms. It was found that with
increasing actinide atomic number, the bond length of terminal multiple
An–N1 bond decreases, in accordance with the actinide contraction.
The Mayer bond order of An–N1 decreases gradually from An =
Pa to Pu, which indicates a decrease in bond strength. The terminal
multiple bond for L–An–N compounds contains one σ
and two π molecular orbitals, and the contributions of the 6d
orbital to covalency are larger in magnitude than the 5f orbital based
on NBO analysis and topological analysis of electron density. This
work may help in understanding of the bonding nature of An–N
multiple bonds and elucidating the trends and electronic structure
changes across the actinide series. It can also shed light on the
construction of novel An–N multiple bonds.