Journal article
Convenient Syntheses of Trivalent Uranium Halide Starting Materials without Uranium Metal
Inorganic chemistry, Vol.60(11), pp.7593-7601
05/13/2021
DOI: 10.1021/acs.inorgchem.1c00598
PMID: 33984231
Abstract
Low-valent uranium coordination chemistry continues to rely heavily on access to trivalent starting materials, but these reagents are typically prepared from uranium turnings, which are becoming increasingly difficult to acquire. Here we report convenient syntheses of UI
(THF)
(THF = tetrahydrofuran) and UBr
(THF)
from UCl
, a more accessible uranium starting material that can be prepared from commercially available uranium oxides. UCl
(THF)
(
), UBr
(THF)
(
), and UI
(THF)
(
) were prepared by single-pot reductions from UCl
using KH and KC
and converted to
or
by halide exchange with the corresponding Me
SiX (where X = Br or I). Reduction of UI
(Et
O)
(
; Et
O = diethyl ether) and UI
(1,4-dioxane)
(
) was also shown to cleanly yield
. Complex
was also synthesized separately by the addition of anhydrous HCl to U(BH
)
(THF)
, which was prepared by thermal reduction of U(BH
)
. All three trivalent uranium halide complexes were isolated in high crystalline yields (typically 85-99%) and their formulations were confirmed by single-crystal X-ray diffraction, elemental analysis, and
H NMR and IR spectroscopy. Elemental analysis conducted on triplicate samples of
-
exposed to vacuum for different time intervals revealed significant THF loss for all three complexes in as little as 15 min. Overall, these results offer expedient entry into low-valent uranium chemistry for researchers lacking access to uranium turnings.
Details
- Title: Subtitle
- Convenient Syntheses of Trivalent Uranium Halide Starting Materials without Uranium Metal
- Creators
- Taylor V Fetrow - Department of Chemistry, The University of Iowa, E331 Chemistry Building, Iowa City, Iowa 52242, United StatesJ Peter Grabow - Department of Chemistry, The University of Iowa, E331 Chemistry Building, Iowa City, Iowa 52242, United StatesJohna Leddy - Department of Chemistry, The University of Iowa, E331 Chemistry Building, Iowa City, Iowa 52242, United StatesScott R Daly - Department of Chemistry, The University of Iowa, E331 Chemistry Building, Iowa City, Iowa 52242, United States
- Resource Type
- Journal article
- Publication Details
- Inorganic chemistry, Vol.60(11), pp.7593-7601
- DOI
- 10.1021/acs.inorgchem.1c00598
- PMID
- 33984231
- NLM abbreviation
- Inorg Chem
- ISSN
- 0020-1669
- eISSN
- 1520-510X
- Grant note
- DOI: 10.13039/100006151, name: Basic Energy Sciences, award: DESC0019426
- Language
- English
- Date published
- 05/13/2021
- Academic Unit
- Chemistry
- Record Identifier
- 9984216720602771
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