Structure and Characterization of an Americium Bis(O,O'-diethyl)dithiophosphate Complex

A facile synthesis of an americium complex with a sulfur-donor ligand has been developed, allowing characterization of americium bonding from multiple perspectives via several techniques. Reaction of ²⁴³Am with S₂P(OEt)₂^- yields the tetrakis complex [Am(S₂P(OEt)₂)₄]^- that can be crystallized as the tetraphenylarsonium salt. Structures obtained from single crystal X-ray diffraction show bond length discrepancies from the neodymium analogue consistent with the soft-donor bond enhancement common to actinides. Solid state optical spectroscopy confirms interaction of the ligand with 5f orbitals. ³¹P nuclear magnetic reflects the minor paramagnetism of Am(III). Computational investigations through CASSCF calculations, ligand-field density functional theory, and quantum chemical topological analysis allow a quantification of covalency or orbital interaction effects via total energy density and nephelauxetic parameters, both of which indicate greater covalency in the americium species than in the neodymium analogue or the americium aquo complex.