Issue 6, 2015

The strength of actinide–element bonds from the quantum theory of atoms-in-molecules

Abstract

[AnX3]2(μ–η22-N2) (An = Th–Pu; X = F, Cl, Br, Me, H, OPh) have been studied using relativistic density functional theory. Geometric and vibrational data suggest that metal→N2 charge transfer maximises at the protactinium systems, which feature the longest N–N bonds and the smallest σ(N–N), as a result of partial population of the N–N π* orbitals. There is very strong correlation of the standard quantum theory of atoms-in-molecules (QTAIM) metrics – bond critical point ρ, ∇2ρ and H and delocalisation indices – with An–N and N–N bond lengths and σ(N–N), but the correlation with An–N interaction energies is very poor. A similar situation exists for the other systems studied; neutral and cationic actinide monoxide and dioxides, and AnL3+ and AnL33+ (L = pyridine (Py), pyrazine (Pz) and triazine (Tz)) with the exception of some of the ∇2ρ data, for which moderate to good correlations with energy data are sometimes seen. By contrast, in almost all cases there is very strong correlation of interaction and bond energies with |ΔQQTAIMAn|, a simple QTAIM metric which measures the amount of charge transferred to or from the actinide on compound formation.

Graphical abstract: The strength of actinide–element bonds from the quantum theory of atoms-in-molecules

Supplementary files

Article information

Article type
Paper
Submitted
31 Jul 2014
Accepted
17 Sep 2014
First published
17 Sep 2014
This article is Open Access
Creative Commons BY license

Dalton Trans., 2015,44, 2554-2566

Author version available

The strength of actinide–element bonds from the quantum theory of atoms-in-molecules

Q. Huang, J. R. Kingham and N. Kaltsoyannis, Dalton Trans., 2015, 44, 2554 DOI: 10.1039/C4DT02323D

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