Structure and Characterization of an Americium Bis(O,O’-diethyl)dithiophosphate Complex
| Autor: | Cory J. Windorff, Alyssa N. Gaiser, Thomas E. Albrecht-Schönzart, R D M Greer, Cristian Celis-Barros, Joseph M. Sperling |
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| Rok vydání: | 2020 |
| Předmět: |
010405 organic chemistry
Ligand Chemistry chemistry.chemical_element Americium 010402 general chemistry 01 natural sciences 0104 chemical sciences Inorganic Chemistry Bond length Paramagnetism Physical chemistry Density functional theory Physical and Theoretical Chemistry Metal aquo complex Spectroscopy Single crystal |
| Zdroj: | Inorganic Chemistry. 59:16291-16300 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/acs.inorgchem.0c02085 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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