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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Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
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TY - JOUR
T1 - Topological study of bonding in aquo and bis(triazinyl)pyridine complexes of trivalent lanthanides and actinides
T2 - does covalency imply stability?
AU - Fryer-Kanssen, Izaak
AU - Austin, Jonathan
AU - Kerridge, Andrew
N1 - 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
PY - 2016/10/17
Y1 - 2016/10/17
N2 - 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.
AB - 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.
U2 - 10.1021/acs.inorgchem.6b0096
DO - 10.1021/acs.inorgchem.6b0096
M3 - Journal article
VL - 55
SP - 10034
EP - 10042
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 20
ER -