Homoleptic Uranium-Bis(acyl)phosphide Complexes

被引：10

作者：

Carpenter, Stephanie H. ^{[2
]}

Wolford, Nikki J. ^{[1
]}

Billow, Brennan S. ^{[2
]}

V. Fetrow, Taylor ^{[2
]}

Cajiao, Nathalia ^{[1
]}

Radovic, Aleksa ^{[1
]}

Janicke, Michael T. ^{[2
]}

Neidig, Michael L. ^{[1
]}

Tondreau, Aaron M. ^{[2
]}

机构：

[1] Univ Rochester, Dept Chem, Rochester, NY 14627 USA

[2] Alamos Natl Lab, Los Alamos, NM 87545 USA

来源：

INORGANIC CHEMISTRY | 2022年 / 61卷 / 32期

关键词：

STRUCTURAL-CHARACTERIZATION; CRYSTAL-STRUCTURE; METALLA-ALLENES; U-IV=C; REACTIVITY; LIGAND; URANIUM(III); THORIUM(IV); CERIUM(IV); PH2PNSIME3;

D O I：

10.1021/acs.inorgchem.2c00639

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The first uranium bis(acyl)phosphide (BAP) complexes were synthesized from the reaction between sod i u m bis(mesitoyl)phosphide (Na((mes)BAP)) or sodium bis(2,4,6-triisopropylbenzoyl)phosphide (Na-((tripp)BAP)) 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((tripp)BAP)3 has a rhombic signal near g = 2 (g(1) = 2.03; g(2 )= 2.01; and g(3) = 1.98) that is consistent with the EPR-observed unpaired electron being located in a molecula r orbital that appears ligand-derived . However, upon warming the complex to room temperature, no resonance was observed, indicating the presence of uranium character.

引用

页码：12508 / 12517

页数：10

共 89 条

[1]

[Anonymous], OLEX 212 COMPL 2014

[2]

[Anonymous], 2010, Bruker Instrument Service, Version 2010.1.0.0

[3]

APEX2, 2010, Data Refinement Software, Version 2010.1-2

[4] Crystal structures and spectroscopic properties of 2λ3-phospha-1,3-dionates and 1,3-dionates of calcium -: Comparative studies on the 1,3-diphenyl and 1,3-Di(tert-butyl) derivatives [J].