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Published on: October 6, 2023
Exploring Metal-Ligand Interactions and Predicting Stability Constants in Uranyl Nitrate Complexes with Alkyl
Vemuri Lakshmi Ganesh1,2, Aditya Ramesh Sachin3, Cherukuri Venkata Siva Brahmananda Rao1,2
1Indira Gandhi Centre for Atomic Research, Kalpakkam, Tamil Nadu 603102, India.
None:
The complexation behavior of various trialkyl phosphates, including symmetrical, partially symmetrical, and unsymmetrical alkyl substituents (methyl, ethyl, propyl, butyl), with uranyl nitrate was investigated using density functional theory. Quantum chemical calculations indicate that, for all ligands (symmetrical, partially symmetrical, and unsymmetrical), the phosphorus and phosphoryl oxygen charges remain nearly identical, reaffirming that individual alkyl substituents do not significantly influence the charges of the phosphoryl (P═O) group. Energy decomposition analysis highlights the role of strain energy resulting from geometric deformations during complex formation. Consequently, complexes of symmetrical ligands exhibit more negative binding energies compared to their unsymmetrical counterparts. The stability constants of all metal complexes studied were predicted using quantum chemical calculations. The predicted stability constant for the TBP complex with uranyl nitrate is 2.3, which aligns closely with the experimental value of 1.9.
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