Homoleptic Uranium–Bis(acyl)phosphide Complexes

Carpenter, Stephanie H.; Wolford, Nikki J.; Billow, Brennan S.; Fetrow, Taylor V.; Cajiao, Nathalia; Radović, Aleksa; Janicke, Michael T.; Neidig, Michael L.; Tondreau, Aaron M.

doi:10.1021/acs.inorgchem.2c00639

Title: Homoleptic Uranium–Bis(acyl)phosphide Complexes

Journal Article · 28 July 2022 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.2c00639 · OSTI ID:1887143

^[1]; Wolford, Nikki J. ^[2];

^[1]; Fetrow, Taylor V. ^[1];

^[2]; Radović, Aleksa ^[2]; Janicke, Michael T. ^[1];

^[2];

^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
University of Rochester, NY (United States)

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.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: 89233218CNA000001; SC0021917

OSTI ID:: 1887143

Report Number(s):: LA-UR-21-28361

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 32 Vol. 61; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
bis(acyl)phosphine
electron paramagnetic resonance
uranium

CCDC 2132475: Experimental Crystal Structure Determination H., Carpenter, Stephanie; J., Wolford, Nikki; S., Billow, Brennan https://doi.org/10.5517/ccdc.csd.cc29l0jg The current record is supplemented by this dataset	dataset	January 2022
CCDC 2132476: Experimental Crystal Structure Determination H., Carpenter, Stephanie; J., Wolford, Nikki; S., Billow, Brennan https://doi.org/10.5517/ccdc.csd.cc29l0kh The current record is supplemented by this dataset	dataset	January 2022
CCDC 2132477: Experimental Crystal Structure Determination H., Carpenter, Stephanie; J., Wolford, Nikki; S., Billow, Brennan https://doi.org/10.5517/ccdc.csd.cc29l0lj The current record is supplemented by this dataset	dataset	January 2022
CCDC 2132478: Experimental Crystal Structure Determination H., Carpenter, Stephanie; J., Wolford, Nikki; S., Billow, Brennan https://doi.org/10.5517/ccdc.csd.cc29l0mk The current record is supplemented by this dataset	dataset	January 2022
CCDC 2132479: Experimental Crystal Structure Determination H., Carpenter, Stephanie; J., Wolford, Nikki; S., Billow, Brennan https://doi.org/10.5517/ccdc.csd.cc29l0nl The current record is supplemented by this dataset	dataset	January 2022
CCDC 2132485: Experimental Crystal Structure Determination H., Carpenter, Stephanie; J., Wolford, Nikki; S., Billow, Brennan https://doi.org/10.5517/ccdc.csd.cc29l0vs The current record is supplemented by this dataset	dataset	January 2022
CCDC 2132486: Experimental Crystal Structure Determination H., Carpenter, Stephanie; J., Wolford, Nikki; S., Billow, Brennan https://doi.org/10.5517/ccdc.csd.cc29l0wt The current record is supplemented by this dataset	dataset	January 2022

Title: Homoleptic Uranium–Bis(acyl)phosphide Complexes

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