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
 

A diuranium carbide cluster stabilized inside a C80 fullerene cage

Journal Article · · Nature Communications
 [1];  [2];  [3];  [2];  [4];  [4];  [5];  [6];  [6];  [6];  [3];  [3];  [7];  [7];  [3];  [3];  [3];  [2];  [4];  [8] more »;  [3] « less
  1. Soochow University, Suzhou, Jiangsu (China); None
  2. Tsinghua Univ., Beijing (China)
  3. Soochow University, Suzhou, Jiangsu (China)
  4. Universität Bonn (Germany)
  5. University of Texas, El Paso, TX (United States)
  6. State Univ. of New York, Buffalo, NY (United States)
  7. Leibniz Institute for Solid State and Materials Research, Dresden (Germany)
  8. Tsinghua Univ., Beijing (China); Universität Siegen (Germany)
+ Show Author Affiliations
Unsupported non-bridged uranium–carbon double bonds have long been sought after in actinide chemistry as fundamental synthetic targets in the study of actinide-ligand multiple bonding. Here we report that, utilizing Ih(7)-C80 fullerenes as nanocontainers, a diuranium carbide cluster, U=C=U, has been encapsulated and stabilized in the form of UCU@Ih(7)-C80. This endohedral fullerene was prepared utilizing the Krätschmer–Huffman arc discharge method, and was then co-crystallized with nickel(II) octaethylporphyrin (NiII-OEP) to produce UCU@Ih(7)-C80·[NiII-OEP] as single crystals. X-ray diffraction analysis reveals a cage-stabilized, carbide-bridged, bent UCU cluster with unexpectedly short uranium–carbon distances (2.03 Å) indicative of covalent U=C double-bond character. The quantum-chemical results suggest that both U atoms in the UCU unit have formal oxidation state of +5. The structural features of UCU@Ih(7)-C80 and the covalent nature of the U(f1)=C double bonds were further affirmed through various spectroscopic and theoretical analyses.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); State Univ. of New York, Buffalo, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC02-05CH11231; SC0001136
OSTI ID:
1511585
Alternate ID(s):
OSTI ID: 1631596
Journal Information:
Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 9; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

References (73)

Triamidoamine-Uranium(IV)-Stabilized Terminal Parent Phosphide and Phosphinidene Complexes journal March 2014
Synthesis, Characterization, and Reactivity of a Uranium(VI) Carbene Imido Oxo Complex journal May 2014
Cation-Cation Interactions, Magnetic Communication, and Reactivity of the Pentavalent Uranium Ion [U(N t Bu) 2 ] + journal May 2009
A Formal High Oxidation State Inverse-Sandwich Diuranium Complex: A New Route to f-Block-Metal Bonds journal September 2011
Dative Bonds in Main-Group Compounds: A Case for More Arrows! journal May 2014
Oxidation State, A Long-Standing Issue! journal March 2015
The Renaissance of Non-Aqueous Uranium Chemistry journal June 2015
Synthesis and Characterization of the D 5 h Isomer of the Endohedral Dimetallofullerene Ce 2 @C 80 : Two-Dimensional Circulation of Encapsulated Metal Atoms Inside a Fullerene Cage journal September 2009
Molecular Double-Bond Covalent Radii for Elements Li–E112 journal November 2009
A Mixed-Valent Uranium Phosphonate Framework Containing U IV , U V , and U VI journal July 2016
Oxo ligand functionalization in the uranyl ion (UO22+) journal February 2010
Matrix preparation and spectroscopic and theoretical investigation of small high oxidation-state complexes of groups 3–12, 14, lanthanide and actinide metal atoms: Carbon-metal single, double and triple bonds journal March 2017
Electrochemistry of Sc3N@C78 and Sc3N@C80 (Ih): On achieving reversible redox waves of the trimetal nitride endohedral fullerenes journal September 2007
Laser melting of uranium carbides journal March 2009
Endohedral Fullerenes journal May 2013
The Inverse Trans Influence in a Family of Pentavalent Uranium Complexes journal June 2014
A uranium-carbon multiple bond. Crystal and molecular structure of (.eta.5-C5H5)3UCHP(CH3)2(C6H5) journal June 1981
Exchange of an Imido Ligand in Bis(imido) Complexes of Uranium journal October 2006
Metal Atoms Collinear with the Spiro Carbon of 6,6-Open Adducts, M 2 @C 80 (Ad) (M = La and Ce, Ad = Adamantylidene) journal January 2008
Synthesis of a Nitrido-Substituted Analogue of the Uranyl Ion, [N═U═O] + journal May 2010
Synthesis of a Phosphorano-Stabilized U(IV)-Carbene via One-Electron Oxidation of a U(III)-Ylide Adduct journal May 2011
Exploring the Uranyl Organometallic Chemistry: From Single to Double Uranium−Carbon Bonds journal April 2011
Probing the Reactivity and Electronic Structure of a Uranium(V) Terminal Oxo Complex journal September 2011
Synthesis of Uranium(VI) Terminal Oxo Complexes: Molecular Geometry Driven by the Inverse Trans -Influence journal March 2012
A Complete Family of Terminal Uranium Chalcogenides, [U(E)(N{SiMe 3 } 2 ) 3 ] − (E = O, S, Se, Te) journal September 2012
Stable Uranium(VI) Methyl and Acetylide Complexes and the Elucidation of an Inverse Trans Influence Ligand Series journal August 2013
Synthesis of Uranium–Ligand Multiple Bonds by Cleavage of a Trityl Protecting Group journal December 2013
Molecular and Electronic Structure of Dinuclear Uranium Bis-μ-Oxo Complexes with Diamond Core Structural Motifs journal July 2014
Use of 77 Se and 125 Te NMR Spectroscopy to Probe Covalency of the Actinide-Chalcogen Bonding in [Th(E n ){N(SiMe 3 ) 2 } 3 ] − (E = Se, Te; n = 1, 2) and Their Oxo-Uranium(VI) Congeners journal January 2016
Unique Four-Electron Metal-to-Cage Charge Transfer of Th to a C 82 Fullerene Cage: Complete Structural Characterization of Th@ C 3 v (8)-C 82 journal March 2017
Solid C60: a new form of carbon journal September 1990
Small-bandgap endohedral metallofullerenes in high yield and purity journal September 1999
Now U=C it journal April 2009
Isolation and characterization of a uranium(VI)–nitride triple bond journal May 2013
Triamidoamine uranium(IV)–arsenic complexes containing one-, two- and threefold U–As bonding interactions journal June 2015
Elucidating bonding preferences in tetrakis(imido)uranate(VI) dianions journal April 2017
Endohedral fullerene with μ3-carbido ligand and titanium-carbon double bond stabilized inside a carbon cage journal April 2014
Metal–ligand multiple bonding in uranium: structure and reactivity journal January 2010
Steric control of redox events in organo-uranium chemistry: synthesis and characterisation of U( v ) oxo and nitrido complexes journal January 2016
Structure and stability of endohedral fullerene Sc3N@C80: A Raman, infrared, and theoretical analysis journal October 2001
Formation of unprecedented actinidecarbon triple bonds in uranium methylidyne molecules journal November 2007
Covalent Uranium Carbene Chemistry journal March 2015
Synthesis of Imido Analogs of the Uranyl Ion journal December 2005
Synthesis and Structure of a Terminal Uranium Nitride Complex journal June 2012
Cation-Cation Interactions, Magnetic Communication, and Reactivity of the Pentavalent Uranium Ion [U(N t Bu) 2 ] + journal May 2009
A Formal High Oxidation State Inverse-Sandwich Diuranium Complex: A New Route to f-Block-Metal Bonds journal September 2011
Electrochemistry and Ab Initio Study of the Dimetallofullerene La2@C80 journal June 1995
Chemical, Electrochemical, and Structural Properties of Endohedral Metallofullerenes journal September 2009
Triamidoamine-Uranium(IV)-Stabilized Terminal Parent Phosphide and Phosphinidene Complexes journal March 2014
Synthesis, Characterization, and Reactivity of a Uranium(VI) Carbene Imido Oxo Complex journal May 2014
The Nature of the UC Double Bond: Pushing the Stability of High-Oxidation-State Uranium Carbenes to the Limit journal April 2013
Progress in molecular uranium-nitride chemistry journal May 2014
A Systematic Theoretical Study of UC 6 : Structure, Bonding Nature, and Spectroscopy journal November 2017
The large range of uranyl bond lengths: ab initio calculations on simple uranium-oxygen clusters journal September 1991
Formation and Characterization of the Uranium Methylidene Complexes CH 2 UHX (X = F, Cl, and Br) journal February 2006
Synthesis, Molecular and Electronic Structure of U V (O)[N(SiMe 3 ) 2 ] 3 journal January 2012
Quasirelativistic Pseudopotential Study of Species Isoelectronic to Uranyl and the Equatorial Coordination of Uranyl journal May 1994
[(MeC5H4)3U]2[.mu.-1,4-N2C6H4]: a bimetallic molecule with antiferromagnetic coupling between the uranium centers journal May 1990
Positional Control of Encapsulated Atoms Inside a Fullerene Cage by Exohedral Addition journal October 2005
Synthesis of a Uranium(VI)-Carbene: Reductive Formation of Uranyl(V)-Methanides, Oxidative Preparation of a [R 2 C═U═O] 2+ Analogue of the [O═U═O] 2+ Uranyl Ion (R = Ph 2 PNSiMe 3 ), and Comparison of the Nature of U IV ═C, U V ═C, and U VI ═C Double Bonds journal June 2012
Synthesis and Spectroscopic and Computational Characterization of the Chalcogenido-Substituted Analogues of the Uranyl Ion, [OUE] 2+ (E = S, Se) journal March 2013
The UC Double Bond: Synthesis and Study of Uranium Nucleophilic Carbene Complexes journal January 2009
Metal–ligand multiple bonding in uranium: structure and reactivity journal January 2010
Steric control of redox events in organo-uranium chemistry: synthesis and characterisation of U( v ) oxo and nitrido complexes journal January 2016
Synthesis and reactivity of a terminal uranium( iv ) sulfide supported by siloxide ligands journal January 2016
Uranium( iv ) terminal hydrosulfido and sulfido complexes: insights into the nature of the uranium–sulfur bond journal January 2016
Single crystal structures and theoretical calculations of uranium endohedral metallofullerenes (U@C 2n , 2n = 74, 82) show cage isomer dependent oxidation states for U journal January 2017
Pentavalent uranium chemistry—synthetic pursuit of a rare oxidation state journal January 2009
Recent developments in actinide–ligand multiple bonding journal January 2013
SIR2004 : an improved tool for crystal structure determination and refinement journal March 2005
WinGX and ORTEP for Windows : an update journal July 2012
Crystal structure refinement with SHELXL journal January 2015
f-Element-metal bond chemistry journal January 2012

Cited By (8)

Double dative bond between divalent carbon(0) and uranium journal November 2018
Purification of Uranium-based Endohedral Metallofullerenes (EMFs) by Selective Supramolecular Encapsulation and Release journal July 2018
Purification of Uranium-based Endohedral Metallofullerenes (EMFs) by Selective Supramolecular Encapsulation and Release journal July 2018
Propeller-Shaped Fe 4 and Fe 3 M Molecular Nanomagnets: A Journey from Crystals to Addressable Single Molecules: Propeller-Shaped Fe 4 and Fe 3 M Molecular Nanomagnets: A Journey from Crystals to Addressable Single Molecules journal January 2019
Small Cage Uranofullerenes: 27 Years after Their First Observation journal April 2019
Robust metal-pentagon interactions in the Th-based endohedral metallofullerenes revealed by DFT calculations journal October 2018
Highly selective encapsulation and purification of U-based C 78 -EMFs within a supramolecular nanocapsule journal January 2019
Trapping an unprecedented Ti 3 C 3 unit inside the icosahedral C 80 fullerene: a crystallographic survey journal January 2019

Similar Records

Diuranium(IV) Carbide Cluster U2C2 Stabilized Inside Fullerene Cages
Journal Article · Sun Dec 01 19:00:00 EST 2019 · Journal of the American Chemical Society · OSTI ID:1596909
Internal And External Factors in the Structural Organization in Cocrystals of the Mixed-Metal Endohedrals (GdSc2N@I(H)-C(80), Gd(2)ScN@I(H)-C(80), And TbSc(2)N@I(H)C(80) ) And Nickel(II) Octaethylporphyrin
Journal Article · Tue May 26 00:00:00 EDT 2009 · Inorg. Chem 47:1420,2008 · OSTI ID:953574

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY