Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 135, Issue 6, Pages 2279-2290Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja310575j
Keywords
-
Categories
Funding
- U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences (Heavy Element Chemistry Program)
- US Department of Energy, Office of Science Undergraduate Internship Program (SULI)
- Glenn T. Seaborg Institute Postdoctoral Fellowship Program
- Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences of the U.S. Department of Energy at Lawrence Berkeley National Laboratory [DE-AC02-05CH11231]
- DOE Office of Biological and Environmental Research
- National Institutes of Health, National Institute of General Medical Sciences [P41GM103393]
- National Nuclear Security Administration of U.S. Department of Energy [DEAC52-06NA25396]
Ask authors/readers for more resources
Synthetic routes to salts containing uranium bisimido tetrahalide anions [U(NR)(2)X-4](2-) (X = Cl-, Br-) and non-coordinating NEt4+ and PPh4+ countercations are reported. In general, these compounds can be prepared from U(NR)(2)I-2(THF)(x) (x = 2 and R = 'Bu, Ph; x = 3 and R = Me) upon addition of excess halide. In addition to providing stable coordination complexes with Cl-, the [U(NMe)(2)](2 +) cation also reacts with Br- to form stable [NEt4](2)[U(NMe)(2)Br-4] complexes. These materials were used as a platform to compare electronic structure and bonding in [U(NR)(2)](2+) with [UO2](2+). Specifically, Cl K-edge X-ray absorption spectroscopy (XAS) and both ground-state and time-dependent hybrid density functional theory (DFT and TDDFT) were used to probe U-Cl bonding interactions in [PPh4](2)[U((NBu)-Bu-t)(2)Cl-4] and [PPh4](2)[UO2Cl4]. The DFT and XAS results show the total amount of Cl 3p character mixed with the U 5f orbitals was roughly 7-10% per U-Cl bond for both compounds, which shows that moving from oxo to imido has little effect on orbital mixing between the U 5f and equatorial Cl 3p orbitals. The results are presented in the context of recent Cl K-edge XAS and DFT studies on other hexavalent uranium chloride systems with fewer oxo or imido ligands.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available