Issue 25, 2011

On the “yl” bond weakening in uranyl(VI) coordination complexes

Abstract

The U–Oyl triple bonds in the UO22+ aquo ion are known to be weakened by replacing the first shell water with organic or inorganic ligands. Weakening of the U–Oyl bond may enhance the reactivity of “yl” oxygens and uranyl(VI) cationcation interactions. Density functional theory calculations as well as previously published vibrational spectroscopic data have been used to study the origin of the U–Oyl bond weakening in uranyl(VI) coordination complexes. Natural population analyses (NPA) revealed that the electron localization on the Oyl 2p orbital is a direct measure of the U–Oyl bond weakening, indicating that the bond weakening is correlated to the weakening of the U–Oyl covalent bond and not that of the ionic bond. The Mulliken analysis gives poor results for uranium to ligand electron partitioning and is thus unreliable. Further analyses of molecular orbitals near the highest occupied molecular orbital (HOMO) show that both the σ and π donating abilities of the ligands may account for the U–Oyl bond weakening. The mechanism of the bond weakening varies with coordinating ligand so that each case needs to be examined independently.

Graphical abstract: On the “yl” bond weakening in uranyl(VI) coordination complexes

Supplementary files

Article information

Article type
Paper
Submitted
22 Mar 2011
Accepted
14 Apr 2011
First published
24 May 2011

Dalton Trans., 2011,40, 6732-6737

On the “yl” bond weakening in uranyl(VI) coordination complexes

S. Tsushima, Dalton Trans., 2011, 40, 6732 DOI: 10.1039/C1DT10481K

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