Abstract
We report the synthesis and characterization of five novel Cd2+/UO22+ heterometallic complexes that feature Cd-oxo distances ranging from 78 to 171% of the sum of the van der Waals radii for these atoms. This work marks an extension of our previously reported Pb2+/UO22+ and Ag+/UO22+ complexes, yet with much more pronounced structural and spectroscopic effects resulting from Cd-oxo interactions. We observe a major shift in the U═O symmetric stretch and significant uranyl bond length asymmetry. The ρbcp values calculated using Quantum Theory of Atoms in Molecules (QTAIM) support the asymmetry displayed in the structural data and indicate a decrease in covalent character in U═O bonds with close Cd-oxo contacts, more so than in related compounds containing Pb2+ and Ag+. Second-order perturbation theory (SOPT) analysis reveals that O spx → Cd s is the most significant orbital overlap and U═O bonding and antibonding orbitals also contribute to the interaction (U═O σ/π → Cd d and Cd s → U═O σ/π*). The overall stabilization energies for these interactions were lower than those in previously reported Pb2+ cations, yet larger than related Ag+ compounds. Analysis of the equatorial coordination sphere of the Cd2+/UO22+ compounds (along with Pb2+/UO22+ complexes) reveals that 7-coordinate uranium favors closer, stronger Mn+-oxo contacts. These results indicate that U═O bond strength tuning is possible with judicious choice of metal cations for oxo interactions and equatorial ligand coordination.
Published Version
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