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Theoretical Investigation on Multiple Bonds in Terminal Actinide Nitride Complexes
journal contribution
posted on 2014-09-15, 00:00 authored by Qun-Yan Wu, Cong-Zhi Wang, Jian-Hui Lan, Cheng-Liang Xiao, Xiang-Ke Wang, Yu-Liang Zhao, Zhi-Fang Chai, Wei-Qun ShiA series
of actinide (An) species of L-An-N compounds [An = Pa–Pu,
L = [N(CH2CH2NSiPri3)3]3–, Pri = CH(CH3)2] 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.