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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 - Assessing covalency in equatorial U-N bonds
T2 - density based measures of bonding in BTP and isoamethyrin complexes of uranyl
AU - Di Pietro, Poppy
AU - Kerridge, Andrew
N1 - © Royal Society of Chemistry 2016
PY - 2016/7/7
Y1 - 2016/7/7
N2 - Calculations performed at the density functional level of theory have been used to investigate complexes of uranyl with the expanded porphyrin isoamethyrin and the bis-triazinyl-pyridine (BTP) ligands, the latter of which is well-known to be effective in the separation of trivalent lanthanides and actinides. Analysis has been performed using a range of density-based techniques, including the Quantum Theory of Atoms in Molecules (QTAIM), the Electron Localisation Function (ELF) and the reduced density gradient (RDG). The effects of peripheral alkyl substituents on UO2-isoamethyrin, known to be vital for proper replication of the experimental geometry, are considered. Evidence for comparable amounts of covalent character has been found in the largely ionic U–N bonds of UO2-isoamethyrin and [UO2(BTP)2]2+ and examination of the variation in the electronic characteristics of the uranyl unit upon complexation in both of these cases reveal striking similarities in the nature of the U–N bonding and the effect of this bonding on the U–Oyl interaction, as well as evidence of donation into the U–N bonding region from the uranyl unit itself.
AB - Calculations performed at the density functional level of theory have been used to investigate complexes of uranyl with the expanded porphyrin isoamethyrin and the bis-triazinyl-pyridine (BTP) ligands, the latter of which is well-known to be effective in the separation of trivalent lanthanides and actinides. Analysis has been performed using a range of density-based techniques, including the Quantum Theory of Atoms in Molecules (QTAIM), the Electron Localisation Function (ELF) and the reduced density gradient (RDG). The effects of peripheral alkyl substituents on UO2-isoamethyrin, known to be vital for proper replication of the experimental geometry, are considered. Evidence for comparable amounts of covalent character has been found in the largely ionic U–N bonds of UO2-isoamethyrin and [UO2(BTP)2]2+ and examination of the variation in the electronic characteristics of the uranyl unit upon complexation in both of these cases reveal striking similarities in the nature of the U–N bonding and the effect of this bonding on the U–Oyl interaction, as well as evidence of donation into the U–N bonding region from the uranyl unit itself.
U2 - 10.1039/c6cp01273f
DO - 10.1039/c6cp01273f
M3 - Journal article
VL - 18
SP - 16830
EP - 16839
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 25
ER -