Rights statement: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright ©2015 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.5b01219
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Final published version
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 - U−Oyl stretching vibrations as a quantitative measure of the equatorial bond covalency in uranyl complexes
T2 - a quantum-chemical investigation
AU - Di Pietro, Poppy
AU - Kerridge, Andrew
N1 - This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright ©2015 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.5b01219
PY - 2016/1/19
Y1 - 2016/1/19
N2 - The molecular structures of a series of uranyl (UO22+) complexes in which the uranium center is equatorially coordinated by a first-row species are calculated at the density functional theory level and binding energies deduced. The resulting electronic structures are investigated using a variety of density-based analysis techniques in order to quantify the degree of covalency in the equatorial bonds. It is shown that a consideration of the properties of both the one-electron and electron-pair densities is required to understand and rationalize the variation in axial bonding effected by equatorial complexation. Strong correlations are found between density-based measures of the covalency and equatorial binding energies, implying a stabilizing effect due to covalent interaction, and it is proposed that uranyl U–Oyl stretching vibrational frequencies can serve as an experimental probe of equatorial covalency.
AB - The molecular structures of a series of uranyl (UO22+) complexes in which the uranium center is equatorially coordinated by a first-row species are calculated at the density functional theory level and binding energies deduced. The resulting electronic structures are investigated using a variety of density-based analysis techniques in order to quantify the degree of covalency in the equatorial bonds. It is shown that a consideration of the properties of both the one-electron and electron-pair densities is required to understand and rationalize the variation in axial bonding effected by equatorial complexation. Strong correlations are found between density-based measures of the covalency and equatorial binding energies, implying a stabilizing effect due to covalent interaction, and it is proposed that uranyl U–Oyl stretching vibrational frequencies can serve as an experimental probe of equatorial covalency.
U2 - 10.1021/acs.inorgchem.5b01219
DO - 10.1021/acs.inorgchem.5b01219
M3 - Journal article
VL - 55
SP - 573
EP - 583
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 2
ER -