Here, the first uranium bis(acyl)phosphide (BAP) complexes were synthesized from the reaction between sodium bis(mesitoyl)phosphide (Na(mesBAP)) or sodium bis(2,4,6-triisopropylbenzoyl)phosphide (Na(trippBAP)) and UI3(1,4-dioxane)1.5. Thermally stable, homoleptic BAP complexes were characterized by single-crystal X-ray diffraction and electron paramagnetic resonance (EPR) spectroscopy, when appropriate, for the elucidation of the electronic structure and bonding of these complexes. EPR spectroscopy revealed that the BAP ligands on the uranium center retain a significant amount of electron density. The EPR spectrum of the trivalent U(trippBAP)3 has a rhombic signal near g = 2 (g1 = 2.03; g2 = 2.01; and g3 = 1.98) that is consistent with the EPR-observed unpaired electron being located in a molecular orbital that appears ligand-derived. However, upon warming the complex to room temperature, no resonance was observed, indicating the presence of uranium character.
@article{osti_1887143,
author = {Carpenter, Stephanie H. and Wolford, Nikki J. and Billow, Brennan S. and Fetrow, Taylor V. and Cajiao, Nathalia and Radović, Aleksa and Janicke, Michael T. and Neidig, Michael L. and Tondreau, Aaron M.},
title = {Homoleptic Uranium–Bis(acyl)phosphide Complexes},
annote = {Here, the first uranium bis(acyl)phosphide (BAP) complexes were synthesized from the reaction between sodium bis(mesitoyl)phosphide (Na(mesBAP)) or sodium bis(2,4,6-triisopropylbenzoyl)phosphide (Na(trippBAP)) and UI3(1,4-dioxane)1.5. Thermally stable, homoleptic BAP complexes were characterized by single-crystal X-ray diffraction and electron paramagnetic resonance (EPR) spectroscopy, when appropriate, for the elucidation of the electronic structure and bonding of these complexes. EPR spectroscopy revealed that the BAP ligands on the uranium center retain a significant amount of electron density. The EPR spectrum of the trivalent U(trippBAP)3 has a rhombic signal near g = 2 (g1 = 2.03; g2 = 2.01; and g3 = 1.98) that is consistent with the EPR-observed unpaired electron being located in a molecular orbital that appears ligand-derived. However, upon warming the complex to room temperature, no resonance was observed, indicating the presence of uranium character.},
doi = {10.1021/acs.inorgchem.2c00639},
url = {https://www.osti.gov/biblio/1887143},
journal = {Inorganic Chemistry},
issn = {ISSN 0020-1669},
number = {32},
volume = {61},
place = {United States},
publisher = {American Chemical Society (ACS)},
year = {2022},
month = {07}}
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES)
