Actinide complexes containing terminal chalcogen ligands involved in multiple bonding with actinide ions are, currently, of high interest, due to both their electronic structures and potential applications in atom transfer chemistry and catalysis. Thanks to these compounds, it is possible to have, for example, selective complexation and separation of actinides in spent nuclear fuel. However, in contrast to the rapidly increasing number of terminal uranium oxo complexes, the number of fully characterized terminal uranium sulfido complexes is quite limited. Thanks to Densitiy Functional Theory (DFT) calculations and Natural Bond Orbitals (NBO) analysis, it's possible to study the bond between uranium and sulfur of these complexes. In this particular case, an atypical strongly polarized triple bond was found in the Uranium(IV) terminal sulfido complex with a triazacyclononane (tacn) based ligand depicted in the figure. Just as it was observed in the experimental measurements, computational analysis showed a big change on the geometry of the complex and the nature of the U-S bond depending if the terminal sulifido complex was capped by hydrogen (the precursor of the terminal sulfido compound).

Terminal Uranium(IV) sulfido and hydrosulfido complexes: Theoretical study of the uranium-sulfur bond

253rd National Meeting (2017)

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