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    Rights statement: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © 2016 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.6b00968

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Topological study of bonding in aquo and bis(triazinyl)pyridine complexes of trivalent lanthanides and actinides: does covalency imply stability?

Research output: Contribution to journalJournal article

Published
<mark>Journal publication date</mark>17/10/2016
<mark>Journal</mark>Inorganic Chemistry
Issue number20
Volume55
Number of pages9
Pages (from-to)10034-10042
Publication statusPublished
Early online date5/08/16
Original languageEnglish

Abstract

The geometrical and electronic structures of Ln[(H2O)9]3+ and [Ln(BTP)3]3+, where Ln = Ce–Lu, have been evaluated at the density functional level of theory using three related exchange-correlation (xc-)functionals. The BHLYP xc-functional was found to be most accurate, and this, along with the B3LYP functional, was used as the basis for topological studies of the electron density via the quantum theory of atoms in molecules (QTAIM). This analysis revealed that, for both sets of complexes, bonding was almost identical across the Ln series and was dominated by ionic interactions. Geometrical and electronic structures of actinide (An = Am, Cm) analogues were evaluated, and [An(H2O)9]3+ + [Ln(BTP)3]3+ → [Ln(H2O)9]3+ + [An(BTP)3]3+ exchange reaction energies were evaluated, revealing Eu ↔ Am and Gd ↔ Cm reactions to favor the An species. Detailed QTAIM analysis of Eu, Gd, Am, and Cm complexes revealed increased covalent character in M–O and M–N bonds when M = An, with this increase being more pronounced in the BTP complexes. This therefore implies a small electronic contribution to An–N bond stability and the experimentally observed selectivity of the BTP ligand for Am and Cm over lanthanides.

Bibliographic note

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © 2016 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.6b00968