Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Uranium Chemistry: Identifying the Next Frontiers

Journal Article · · Inorganic Chemistry
 [1];  [1];  [1]
  1. Texas Tech Univ., Lubbock, TX (United States)
+ Show Author Affiliations
While uranium is the most extensively studied actinide in terms of chemical properties, there remains much to be explored about its fundamental chemistry. Organometallic and organoactinide chemistry first emerged in the 1950s with research that found inspiration from transition-metal chemistry with the synthesis and characterization of uranocene, expanding new opportunities for organoactinide chemistry. Since then, a significant amount of research has pursued many avenues characterizing the fundamental nature of the f orbitals and their modes of bonding as well as their potential in catalysis. Uranium(III/IV) arene complexes dominate much of uranium organometallic chemistry, with bonding interactions stabilized by δ-back-bonding. Recent additions to this area of chemistry include the first UI and new additions of UII organouranium compounds. Uranium–transition metal complexes are still rare and maintain UIV oxidation states, with variable bond lengths determining the transition-metal oxidation state. Resultant reactivities are discussed as synthetic complexes, and unique bonding and coordination motifs are highlighted. In conclusion, this Viewpoint will focus on significant developments in uranium chemistry from the last 15 years while considering key areas for future research.
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)
Grant/Contract Number:
89233218CNA000001
OSTI ID:
2477795
Report Number(s):
LA-UR--24-20089
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 2 Vol. 64; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (101)

Formal Three-Electron Reduction by an f-Element Complex: Formation of [{(C5Me5)(C8H8)U}2(C8H8)] from Cyclooctatetraene and [(C5Me5)3U] journal January 2000
Activation of Small Molecules by Molecular Uranium Complexes book April 2014
cyclo-P5 as Complex Ligand—the Phosphorus Analogue of the Cyclopentadienyl Ligand journal April 1986
Multiple-Bond Metathesis Mediated by Sterically Pressured Uranium Complexes journal April 2006
Lanthanum Does Form Stable Molecular Compounds in the +2 Oxidation State journal February 2008
Facile Conversion of CO/H2 into Methoxide at a Uranium(III) Center journal June 2011
Synthesis and Characterization of a Uranium(II) Monoarene Complex Supported by δ  Backbonding journal May 2014
The Renaissance of Non-Aqueous Uranium Chemistry journal June 2015
An Inverted-Sandwich Diuranium μ-η 5 :η 5 -Cyclo-P 5 Complex Supported by U-P 5 δ-Bonding journal April 2015
Cooperative Crystallization of Heterometallic Indium-Chromium Metal-Organic Polyhedra and Their Fast Proton Conductivity journal May 2015
Uranocenium: Synthesis, Structure, and Chemical Bonding journal June 2019
Charge‐Shift Bonding: A New and Unique Form of Bonding journal November 2019
Isolation of a Perfectly Linear Uranium(II) Metallocene journal February 2020
f‐Element Half‐Sandwich Complexes: A Tetrasilylcyclobutadienyl–Uranium(IV)–Tris(tetrahydroborate) Anion Pianostool Complex journal December 2019
Delivery of a Masked Uranium(II) by an Oxide‐Bridged Diuranium(III) Complex journal December 2020
Facile Synthesis of Uranium Complexes with a Pendant Borane Lewis Acid and 1,2‐Insertion of CO into a U−N Bond journal November 2022
A Route to Stabilize Uranium(II) and Uranium(I) Synthons in Multimetallic Complexes journal April 2023
Expanding the Chemistry of Molecular U 2+ Complexes: Synthesis, Characterization, and Reactivity of the {[C 5 H 3 (SiMe 3 ) 2 ] 3 U} − Anion journal December 2015
Evaluating Electron‐Transfer Reactivity of Complexes of Actinides in +2 and +3 Oxidation States by using EPR Spectroscopy journal January 2020
Covalency in Actinide Compounds journal January 2021
Small-Molecule Activation at Uranium(III) journal April 2013
A single-crystal neutron and X-ray diffraction study of elbaite journal June 2012
Half-sandwich and mixed-ring uranium complexes journal October 1994
Synthesis of a highly strained uranacycle: molecular structures of organometallic products arising from reduction, oxidation and protonolysis journal December 1999
Inverted sandwich arene complexes of uranium journal June 2015
Selective hydroboration of terminal alkynes catalyzed by heterometallic clusters with uranium–metal triple bonds journal May 2022
Nonaqueous Electrochemistry of Uranium Complexes: A Guide to Structure–Reactivity Tuning journal May 2023
Organometallic Neptunium Chemistry journal August 2017
Paramagnetic Metal–Metal Bonded Heterometallic Complexes journal February 2020
Density Functional Theory Analysis of the Importance of Coordination Geometry for 5f 3 6d 1 versus 5f 4 Electron Configurations in U(II) Complexes journal October 2021
Uranium Going the Soft Way: Low-Valent Uranium(III) Coordinated to an Arene-Anchored Tris-Thiophenolate Ligand journal October 2021
Perplexing EPR Signals from 5f36d1 U(II) Complexes journal January 2024
Extending Stannyl Anion Chemistry to the Actinides: Synthesis and Characterization of a Uranium–Tin Bond journal May 2016
Utility of Lithium in Rare-Earth Metal Reduction Reactions to Form Nontraditional Ln 2+ Complexes and Unusual [Li(2.2.2-cryptand)] 1+ Cations journal February 2018
Chelate-Free Synthesis of the U(II) Complex, [(C 5 H 3 (SiMe 3 ) 2 ) 3 U] 1– , Using Li and Cs Reductants and Comparative Studies of La(II) and Ce(II) Analogs journal August 2018
Structural, Electrochemical, and Magnetic Studies of Bulky Uranium(III) and Uranium(IV) Metallocenes journal November 2019
An N -Tethered Uranium(III) Arene Complex and the Synthesis of an Unsupported U–Fe Bond journal July 2017
Catalytic Hydroboration of Esters by Versatile Thorium and Uranium Amide Complexes journal December 2021
Metal–Metal Bonds in Catalysis journal December 2016
Transition Metal Frustrated Lewis Pairs journal October 2013
Uranium(III) Complexes with Bulky Aryloxide Ligands Featuring Metal–Arene Interactions and Their Reactivity Toward Nitrous Oxide journal August 2013
A New Tripodal Ligand System with Steric and Electronic Modularity for Uranium Coordination Chemistry journal October 2009
Exploring the Actinide−Actinide Bond:  Theoretical Studies of the Chemical Bond in Ac 2 , Th 2 , Pa 2 , and U 2 journal December 2006
Completing the Series of +2 Ions for the Lanthanide Elements: Synthesis of Molecular Complexes of Pr 2+ , Gd 2+ , Tb 2+ , and Lu 2+ journal May 2013
Identification of the +2 Oxidation State for Uranium in a Crystalline Molecular Complex, [K(2.2.2-Cryptand)][(C 5 H 4 SiMe 3 ) 3 U] journal August 2013
Photochemical Route to Actinide-Transition Metal Bonds: Synthesis, Characterization and Reactivity of a Series of Thorium and Uranium Heterobimetallic Complexes journal February 2014
Multi-Electron Reduction from Alkyl/Hydride Ligand Combinations in U 4+ Complexes journal September 2008
Bis(arene) Actinide Sandwich Complexes, (η 6 -C 6 H 3 R 3 ) 2 An:  Linear or Bent? journal November 1999
Arene-Bridged Diuranium Complexes:  Inverted Sandwiches Supported by δ Backbonding journal June 2000
UCN@ C s (6)-C 82 : An Encapsulated Triangular UCN Cluster with Ambiguous U Oxidation State [U(III) versus U(I)] journal September 2021
A Uranium(II) Arene Complex That Acts as a Uranium(I) Synthon journal November 2021
Identification of Oxidation State +1 in a Molecular Uranium Complex journal September 2022
Multielectron Redox Chemistry of Uranium by Accessing the +II Oxidation State and Enabling Reduction to a U(I) Synthon journal July 2023
Synthesis and Characterization of U≡C Triple Bonds in Fullerene Compounds journal November 2023
Frustrated Lewis Pairs journal August 2015
Metal–Metal Bonding in Uranium–Group 10 Complexes journal March 2016
Identification of the Formal +2 Oxidation State of Plutonium: Synthesis and Characterization of {Pu II [C 5 H 3 (SiMe 3 ) 2 ] 3 } − journal March 2017
U 2 @ I h (7)-C 80 : Crystallographic Characterization of a Long-Sought Dimetallic Actinide Endohedral Fullerene journal January 2018
Identification of the Formal +2 Oxidation State of Neptunium: Synthesis and Structural Characterization of {Np II [C 5 H 3 (SiMe 3 ) 2 ] 3 } 1– journal May 2018
Synthesis and Characterization of a Neutral U(II) Arene Sandwich Complex journal November 2018
Diuranium(IV) Carbide Cluster U 2 C 2 Stabilized Inside Fullerene Cages journal December 2019
From Chemical Curiosities and Trophy Molecules to Uranium-Based Catalysis: Developments for Uranium Catalysis as a New Facet in Molecular Uranium Chemistry journal May 2021
Synthesis and X-ray Crystal Structure of a Urana[1]ferrocenophane, the First Tris(1,1‘-ferrocenylene) Metal Compound journal October 2000
Preparation and structure of [U2(C6Me6)2Cl7]+, the first uranium(IV) complex with a neutral arene in .eta.6-coordination journal May 1985
Uranocene. The First Member of a New Class of Organometallic Derivatives of the f Elements journal July 2004
Investigations of the Electronic Structure of Arene-Bridged Diuranium Complexes journal January 2013
Actinide Hydride Complexes as Multielectron Reductants:  Analogous Reduction Chemistry from [(C 5 Me 5 ) 2 UH] 2 , [(C 5 Me 5 ) 2 UH 2 ] 2 , and [(C 5 Me 5 ) 2 ThH 2 ] 2 journal July 2007
A Weak Interaction between Iron and Uranium in Uranium Alkyl Complexes Supported by Ferrocene Diamide Ligands journal March 2008
Superconductivity on the border of itinerant-electron ferromagnetism in UGe2 journal August 2000
Coexistence of superconductivity and ferromagnetism in URhGe journal October 2001
Quantum chemical calculations show that the uranium molecule U2 has a quintuple bond journal February 2005
Uranium-mediated electrocatalytic dihydrogen production from water journal January 2016
Strongly coupled binuclear uranium–oxo complexes from uranyl oxo rearrangement and reductive silylation journal February 2012
The role of uranium–arene bonding in H2O reduction catalysis journal December 2017
The secret is in the ring journal February 2018
Reductive assembly of cyclobutadienyl and diphosphacyclobutadienyl rings at uranium journal August 2013
Evidence for single metal two electron oxidative addition and reductive elimination at uranium journal December 2017
A diuranium carbide cluster stabilized inside a C80 fullerene cage journal July 2018
Terminal uranium(V)-nitride hydrogenations involving direct addition or Frustrated Lewis Pair mechanisms journal January 2020
A charged diatomic triple-bonded U≡N species trapped in C82 fullerene cages journal November 2022
Accessing five oxidation states of uranium in a retained ligand framework journal August 2023
Relativistic quantum chemical calculations show that the uranium molecule U2 has a quadruple bond journal October 2018
Transition-metal-bridged bimetallic clusters with multiple uranium–metal bonds journal January 2019
Carbon oxygenate transformations by actinide compounds and catalysts journal January 2017
Inverse cycloheptatrienyl sandwich complexes. Crystal structure of [U(BH 4 ) 2 (OC 4 H 8 ) 5 ][(BH 4 ) 3 U(µ-η 7 ,η 7 -C 7 H 7 )U(BH 4 ) 3 ] journal January 1994
Synthesis and crystal structure of [K(C 12 H 24 O 6 )][U(η-C 7 H 7 ) 2 ], the first cycloheptatrienyl sandwich compound journal January 1995
Radical anionic versus neutral 2,2′-bipyridyl coordination in uranium complexes supported by amide and ketimide ligands journal January 2015
Synthesis, structure, and reactivity of crystalline molecular complexes of the {[C 5 H 3 (SiMe 3 ) 2 ] 3 Th} 1− anion containing thorium in the formal +2 oxidation state journal January 2015
A versatile route to homo- and hetero-bimetallic 5f–5f and 3d–5f complexes supported by a redox active ligand framework journal January 2017
Anion-encapsulating fullerenes behave as large anions: a DFT study journal January 2018
The synthesis and versatile reducing power of low-valent uranium complexes journal January 2020
Heterometallic multinuclear nodes directing MOF electronic behavior journal January 2020
Single metal four-electron reduction by U( ii ) and masked “U( ii )” compounds journal January 2021
Recent advances in heterometallic clusters with f-block metal–metal bonds: synthesis, reactivity and applications journal January 2022
Compounds with low-valent group 13 metals as ligands for electron poor main group and transition metals journal January 2009
Uranium-mediated activation of small molecules journal January 2011
On the maximum bond multiplicity of carbon: unusual C≣U quadruple bonding in molecular CUO journal January 2012
Silicon in organic synthesis journal January 1978
Identification of a uranium–rhodium triple bond in a heterometallic cluster journal August 2019
Unconventional superconductivity in UTe 2 journal April 2022
Reductive Cyclotrimerization of Carbon Monoxide to the Deltate Dianion by an Organometallic Uranium Complex journal February 2006

Figures / Tables (20)

Figure 12(p. 12)figure Figure 12
Figure 5(p. 6)figure Figure 5
Figure 3(p. 5)figure Figure 3
Figure 8(p. 9)figure Figure 8
Figure 13(p. 12)figure Figure 13
Figure 4(p. 5)figure Figure 4
Figure 16(p. 14)figure Figure 16
Figure 11(p. 11)figure Figure 11
Figure 10(p. 11)figure Figure 10
Figure 9(p. 10)figure Figure 9
Figure 14(p. 13)figure Figure 14
Figure 1(p. 3)figure Figure 1
Scheme 2(p. 7)figure Scheme 2
Scheme 3(p. 7)figure Scheme 3
Scheme 4(p. 13)figure Scheme 4
Figure 6(p. 6)figure Figure 6
Scheme 1(p. 3)figure Scheme 1
Figure 15(p. 13)figure Figure 15
Figure 7(p. 8)figure Figure 7
Figure 2(p. 4)figure Figure 2

Similar Records

Reactions of Th Atoms with CO: The First Thorium Carbonyl Complex and an Unprecedented Bent Triplet Insertion Product
Journal Article · Tue Dec 28 23:00:00 EST 1999 · Journal of the American Chemical Society · OSTI ID:15004170
Probing the chemistry, electronic structure and redox energetics in pentavalent organometallic actinide complexes
Journal Article · Mon Dec 31 23:00:00 EST 2007 · Inorganic Chemistry · OSTI ID:960498
Homoleptic Aryl Complexes of Uranium (IV)
Journal Article · Sun Jun 23 20:00:00 EDT 2019 · Angewandte Chemie (International Edition) · OSTI ID:1610533

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY