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Title: Tuning the Oxidation State, Nuclearity, and Chemistry of Uranium Hydrides with Phenylsilane and Temperature: The Case of the Classic Uranium(III) Hydride Complex [(C5 Me 5)2U(μ-H)]2

Journal Article · · Organometallics
 [1];  [2];  [3];  [4];  [4];  [5];  [4]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Vermont, Burlington, VT (United States). Dept. of Chemistry
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Nevada, Las Vegas, NV (United States). Dept. of Chemistry
  3. Univ. of Nevada, Las Vegas, NV (United States). Dept. of Chemistry
  4. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  5. Univ. of Vermont, Burlington, VT (United States). Dept. of Chemistry
+ Show Author Affiliations

Here, this work demonstrates that the oxidation state and chemistry of uranium hydrides can be tuned with temperature and the stoichiometry of phenylsilane. The trivalent uranium hydride [(C5Me5)2U–H]x (5) was found to be comprised of an equilibrium mixture of U(III) hydrides in solution at ambient temperature. A single U(III) species can be selectively prepared by treating (C5Me5)2UMe2 (4) with 2 equiv of phenylsilane at 50 °C. The U(III) system is a potent reducing agent and displayed chemistry distinct from the U(IV) system [(C5Me5)2U(H)(μ-H)]2 (2), which was harnessed to prepare a variety of organometallic complexes, including (C5Me5)2U(dmpe)(H) (6), and the novel uranium(IV) metallacyclopentadiene complex (C5Me5)2U(C4Me4) (11).

Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS) (SC-27); USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF); US Department of Homeland Security (DHS)
Grant/Contract Number:
AC52-06NA25396
OSTI ID:
1400122
Report Number(s):
LA-UR--15-28978
Journal Information:
Organometallics, Journal Name: Organometallics Journal Issue: 5 Vol. 35; ISSN 0276-7333
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (25)

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Organometallic Complexes of Bulky, Optically Active, C 3 -Symmetric Tris(4 S -isopropyl-5,5-dimethyl-2-oxazolinyl)phenylborate (To P *) journal July 2015
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What a Difference a 5f Element Makes: Trivalent and Tetravalent Uranium Halide Complexes Supported by One and Two Bis[2-(diisopropylphosphino)-4-methylphenyl]amido (PNP) Ligands journal March 2009
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Tetravalent and Pentavalent Uranium Acetylide Complexes Prepared by Oxidative Functionalization with CuCCPh journal July 2008
Mono(pentamethylcyclopentadienyl)uranium(III) Complexes:  Synthesis, Properties, and X-ray Structures of (η-C 5 Me 5 )UI 2 (THF) 3 , (η-C 5 Me 5 )UI 2 (py) 3 , and (η-C 5 Me 5 )U[N(SiMe 3 ) 2 ] 2 journal February 2000
Uranium azide photolysis results in C–H bond activation and provides evidence for a terminal uranium nitride journal July 2010
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Cited By (9)

Reversible Dihydrogen Activation and Hydride Transfer by a Uranium Nitride Complex journal March 2018
Reversible Dihydrogen Activation and Hydride Transfer by a Uranium Nitride Complex journal March 2018
Investigation of N-Heterocyclic Carbene-Supported Group 12 Triflates as Pre-catalysts for Hydrosilylation/Borylation journal October 2016
A Sterically Biased Unsymmetrical Azobenzene Derivative: Synthesis, Molecular Structure, and 15N NMR Spectroscopic Analysis of (E)-1-(2,6-Diisopropylphenyl)-2-phenyldiazine journal October 2017
Actinide 2-metallabiphenylenes that satisfy Hückel’s rule journal February 2020
Intrinsic reactivity of a uranium metallacyclopropene toward unsaturated organic molecules journal January 2016
Preparation of a uranium metallacyclocumulene and its reactivity towards unsaturated organic molecules journal January 2017
Recent developments in actinide metallacycles journal January 2018
A sulphur and uranium fiesta! Synthesis, structure, and characterization of neutral terminal uranium( vi ) monosulphide, uranium( vi ) η 2 -disulphide, and uranium( iv ) phosphine sulphide complexes journal January 2019

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38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY