DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: The duality of electron localization and covalency in lanthanide and actinide metallocenes

Journal Article · · Chemical Science
DOI: https://doi.org/10.1039/C9SC06114B · OSTI ID:1599477

Unequivocal experimental evidence for carbon 2p and cerium 4f orbital mixing in cerocene, Ce(C8H8)2is provided from carbon K-edge and Ce M5,4-edge X-ray absorption spectroscopies and corroborated with DFT and configuration interaction calculations.

Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF)
Grant/Contract Number:
89233218CNA000001; AC02-05CH11231; AC52-06NA25396
OSTI ID:
1599477
Alternate ID(s):
OSTI ID: 1756326; OSTI ID: 1634954
Journal Information:
Chemical Science, Journal Name: Chemical Science Journal Issue: 10 Vol. 11; ISSN 2041-6520; ISSN CSHCBM
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United Kingdom
Language:
English

References (149)

Uranium–Ligand Multiple Bonding in Uranyl Analogues, [L═U═L] n + , and the Inverse Trans Influence journal December 2012
Covalency Trends in Group IV Metallocene Dichlorides. Chlorine K-Edge X-Ray Absorption Spectroscopy and Time Dependent-Density Functional Theory journal June 2008
Exchange coupling and magnetic blocking in dilanthanide complexes bridged by the multi-electron redox-active ligand 2,3,5,6-tetra(2-pyridyl)pyrazine journal January 2014
Heavy fermion semiconductors journal May 2000
Lanthanide Photocatalysis journal October 2018
Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide journal May 1994
Ground state calculations of di‐π‐cyclooctatetraene cerium journal February 1991
Ab initio pseudopotentials for Hg through Rn : I. Parameter sets and atomic calculations journal December 1991
Carbon K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory Examination of Metal–Carbon Bonding in Metallocene Dichlorides journal September 2013
Photoelectron spectroscopy of Ce(η-C5H5)3 – Accessing two ion states on 4f ionization journal December 2006
Uranocenes with hydrocarbon substituents journal May 1973
Single but Stronger UO, Double but Weaker UNMe Bonds:  The Tale Told by Cp 2 UO and Cp 2 UNR journal September 2007
Unprecedented Bending and Rearrangement of f-Element Sandwich Complexes Induced by Superbulky Cyclooctatetraenide Ligands journal February 2011
Formally tetravalent cerium and thorium compounds: a configuration interaction study of cerocene Ce(C8H8)2 and thorocene Th(C8H8)2 using energy-adjusted quasirelativistic ab initio pseudopotentials journal June 1995
Is there a molecular analogue of a Kondo singlet state? journal September 1989
The Theory of Atomic Structure and Spectra book December 1981
Ground States, Excited States, and Metal−Ligand Bonding in Rare Earth Hexachloro Complexes:  A DFT-Based Ligand Field Study journal April 2005
Uranium Tetrakis-Aryloxide Derivatives Supported by Tetraazacyclododecane: Synthesis of Air-Stable, Coordinatively-Unsaturated U(IV) and U(V) Complexes journal November 2016
Determining Relative f and d Orbital Contributions to M–Cl Covalency in MCl 6 2– (M = Ti, Zr, Hf, U) and UOCl 5 Using Cl K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory journal March 2012
Intermediate-Valence Tautomerism in Decamethylytterbocene Complexes of Methyl-Substituted Bipyridines journal December 2010
Structural criteria for the mode of bonding of organoactinides and -lanthanides and related compounds journal August 1980
Evidence for 5d-σ and 5d-π covalency in lanthanide sesquioxides from oxygen K-edge X-ray absorption spectroscopy journal January 2016
Synthesis and Properties of Di-π-[8]annulenecerium(IV), Cerocene journal September 2004
Bis(permethylpentalene)cerium ? another ambiguity in lanthanide oxidation state journal January 2007
A complete basis set model chemistry. II. Open‐shell systems and the total energies of the first‐row atoms journal May 1991
Soft X-ray microscopy and spectroscopy at the molecular environmental science beamline at the Advanced Light Source journal February 2006
Pentavalent Curium, Berkelium, and Californium in Nitrate Complexes: Extending Actinide Chemistry and Oxidation States journal July 2018
f-Orbital covalency in the actinocenes (An = Th–Cm): multiconfigurational studies and topological analysis journal January 2014
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
Low-lying electronic states of lanthanocenes and actinocenes M(C8H8)2 (M=Nd, Tb, Yb, U) journal September 1997
Covalency in f-element complexes journal January 2013
Ion pair complex formed between bis(cyclooctatetraenyl)cerium(III) anion and an ether-coordinated potassium cation. Crystal and molecular structure of [K(CH3OCH2CH2)2O][Ce(C8H8)2] journal December 1972
Comparison of non-relativistic and quasi-relativistic SCF-Xα scattered-wave calculations of uranocene, thorocene and cerocene journal June 1984
Bis(cyclooctatetraenyl)uranium (uranocene). A new class of sandwich complexes that utilize atomic f orbitals journal December 1968
Two interpretations of the cerocene electronic ground state journal February 2014
Reversible Sigma C–C Bond Formation Between Phenanthroline Ligands Activated by (C 5 Me 5 ) 2 Yb journal June 2014
Cerium(III) and Cerium(IV) Bis(η 8 -pentalene) Sandwich Complexes:  Synthetic, Structural, Spectroscopic, and Theoretical Studies journal June 2007
Theory of core-level spectroscopy of rare-earth oxides journal December 1992
Scrutinizing metal–ligand covalency and redox non-innocence via nitrogen K-edge X-ray absorption spectroscopy journal January 2019
The Oxidation State of Ce in the Sandwich Molecule Cerocene journal January 1996
Multiplet effects in X-ray spectroscopy journal January 2005
Comparisons of lanthanide/actinide +2 ions in a tris(aryloxide)arene coordination environment journal January 2017
Design, Isolation, and Spectroscopic Analysis of a Tetravalent Terbium Complex journal July 2019
A relativistic lcao hartree-fock-slater investigation of the electronic structure of the actinocenes M(COT)2, M = Th, Pa, U, Np AND Pu journal June 1988
Are the Ground States of the Later Actinocenes Multiconfigurational? All-Electron Spin−Orbit Coupled CASPT2 Calculations on An(η 8 -C 8 H 8 ) 2 (An = Th, U, Pu, Cm) journal July 2009
New evidence for 5f covalency in actinocenes determined from carbon K-edge XAS and electronic structure theory journal January 2014
An investigation of the electronic structure of bis(η-cyclo-octatetraene)-actinoids by helium-( I ) and -( II ) photoelectron spetroscopy journal January 1977
Modeling the electronic states and magnetic properties derived from the f 1 configuration in lanthanocene and actinocene compounds journal January 2017
Charge control of the inverse trans-influence journal January 2015
Magnetic Properties of a Terbium-[1]Ferrocenophane Complex: Analogies between Lanthanide-Ferrocenophane and Lanthanide-Bis-phthalocyanine Complexes journal June 2018
Using solution- and solid-state S K-edge X-ray absorption spectroscopy with density functional theory to evaluate M–S bonding for MS 4 2− (M = Cr, Mo, W) dianions journal January 2014
Synthesis and Characterization of Tris-chelate Complexes for Understanding f -Orbital Bonding in Later Actinides journal January 2019
Spectrum analysis of U 3+ :LaCl 3 journal May 1980
Quantifying the σ and π Interactions between U(V) f Orbitals and Halide, Alkyl, Alkoxide, Amide and Ketimide Ligands journal July 2013
Covalency in the 4f Shell of tris -Cyclopentadienyl Ytterbium (YbCp 3 )—A Spectroscopic Evaluation journal December 2011
Covalency in AnCp4 (An = Th–Cm): a comparison of molecular orbital, natural population and atoms-in-molecules analyses journal January 2010
Reduction of a Cerium(III) Siloxide Complex To Afford a Quadruple-Decker Arene-Bridged Cerium(II) Sandwich journal November 2017
Uncovering f-element bonding differences and electronic structure in a series of 1 : 3 and 1 : 4 complexes with a diselenophosphinate ligand journal January 2013
A method for normalization of X-ray absorption spectra journal June 2005
Does Covalency Increase or Decrease across the Actinide Series? Implications for Minor Actinide Partitioning journal June 2012
Is Cerocene Really a Ce(III) Compound? All-Electron Spin−Orbit Coupled CASPT2 Calculations on M(η 8 -C 8 H 8 ) 2 (M = Th, Pa, Ce) journal March 2009
L 3 and M 4,5 absorption edges of intermediate valent cerium unravelled by resonant photoemission and resonant Auger spectroscopy journal May 1999
Pressure-induced changes in L III x-ray-absorption near-edge structure of Ce O 2 and Ce F 4 : Relevance to 4 f -electronic structure journal November 1988
A Theoretical Study on Divalent Heavier Group 14 Complexes as Promising Donor Ligands for Building Uranium–Metal Bonds journal April 2019
Covalency in CeIV and UIV Halide and N-Heterocyclic Carbene Bonds journal July 2010
Quantitative Evidence for Lanthanide-Oxygen Orbital Mixing in CeO 2 , PrO 2 , and TbO 2 journal November 2017
Covalency in the actinide dioxides: Systematic study of the electronic properties using screened hybrid density functional theory journal July 2007
3d x-ray-absorption lines and the 3 d 9 4 f n + 1 multiplets of the lanthanides journal October 1985
Covalency in Metal–Oxygen Multiple Bonds Evaluated Using Oxygen K-edge Spectroscopy and Electronic Structure Theory journal January 2013
Cerocene Revisited: The Electronic Structure of and Interconversion Between Ce 2 (C 8 H 8 ) 3 and Ce(C 8 H 8 ) 2 journal February 2009
Covalency in f-element bonds journal October 2002
Cerium(IV) Imido Complexes: Structural, Computational, and Reactivity Studies journal February 2017
Zur Elektronenstruktur metallorganischer Komplexe der f-Elemente LXI. Welche Oxidationszahl hat Cer im tiefvioletten 1,1′,4,4′-Tetrakis(trimethylsilyl)cerocen? journal April 2005
On the Upper Limits of Oxidation States in Chemistry journal February 2018
All-electron CASPT2 study of Ce(η8–C8H6)2 journal June 2010
A Macrocyclic Chelator That Selectively Binds Ln 4+ over Ln 3+ by a Factor of 10 29 journal June 2016
M ‐edge x‐ray absorption spectroscopy of 4 f instabilities in rare‐earth systems (invited) journal March 1984
Fine-tuning the Local Symmetry to Attain Record Blocking Temperature and Magnetic Remanence in a Single-Ion Magnet journal March 2014
Emergence of comparable covalency in isostructural cerium( iv )– and uranium( iv )–carbon multiple bonds journal January 2016
Electron Localization in the Ground State of the Ruthenium Blue Dimer journal June 2007
Decamethylytterbocene Complexes of Bipyridines and Diazabutadienes: Multiconfigurational Ground States and Open-Shell Singlet Formation journal May 2009
Photoelectron spectra and bonding in cerocene, bis(.pi.-[8]annulene)cerium(IV) journal December 1985
A proper account of core-polarization with pseudopotentials: single valence-electron alkali compounds journal July 1982
Comparative studies of quasi-relativistic density functional methods for the description of lanthanide and actinide complexes journal May 2003
An Efficient Access to Organocerium(IV) Complexes: Synthesis and Structure of Bis[1,3,6-tris(trimethylsilyl)cyclooctatetraene]cerium(IV) journal September 1994
The study of actinide chemistry with multiconfigurational quantum chemical methods journal January 2011
Variable Photon Energy Photoelectron Spectroscopy and Magnetism of YbCp 3 and LuCp 3 † journal November 2010
Kondo resonance in a single-molecule transistor journal June 2002
Investigations of the Electronic Structure of Arene-Bridged Diuranium Complexes journal January 2013
3 d resonant photoemission spectra at the Ce L 3 edge of CeRh 3 journal September 2000
Molecular Complex of Tb in the +4 Oxidation State journal June 2019
Pyrazolates advance cerium chemistry: a Ce III /Ce IV redox equilibrium with benzoquinone journal January 2017
Bonding and Charge Transfer in Nitrogen-Donor Uranyl Complexes: Insights from NEXAFS Spectra journal October 2014
Covalency in bis([8]annulene)uranium from photoelectron spectroscopy with variable photon energy journal March 1989
Covalency in Lanthanides. An X-ray Absorption Spectroscopy and Density Functional Theory Study of LnCl 6 x ( x = 3, 2) journal February 2015
A Pseudotetrahedral Uranium(V) Complex journal June 2018
4f occupation and hybridization from M-shell excitations in Rare-Earth materials journal February 1985
Probing the Reactivity of the Ce═O Multiple Bond in a Cerium(IV) Oxo Complex journal May 2016
Spectator and participator processes in the resonant photon-in and photon-out spectra at the Ce L3 edge of CeO2 journal July 2012
Application of the Hubbard Model to Cp* 2 Yb(bipy), a Model System for Strong Exchange Coupling in Lanthanide Systems journal September 2012
Flipping the Oxidation State Formalism: Charge Distribution in Organometallic Complexes As Reported by Carbon Monoxide journal January 2017
Relativistic Density Functional Study of the Geometry, Electronic Transitions, Ionization Energies, and Vibrational Frequencies of Protactinocene, Pa(η 8 -C 8 H 8 ) 2 journal November 1998
Oxidation state and covalency in f-element metallocenes (M = Ce, Th, Pu): a combined CASSCF and topological study journal January 2013
Coulomb blockade and the Kondo effect in single-atom transistors journal June 2002
Towards understanding of lanthanide–transition metal bonding: investigations of the first Ce–Fe bonded complex journal January 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
Tetravalent cerium carbene complexes journal January 2007
The CTM4XAS program for EELS and XAS spectral shape analysis of transition metal L edges journal October 2010
Core Level Spectroscopy of Solids book January 2008
Self-Contained Kondo Effect in Single Molecules journal December 2005
Energy-Degeneracy-Driven Covalency in Actinide Bonding journal December 2018
Wasserstoff-Verschiebungen, II. Über das thermische Gleichgewicht zwischen Cyclooctatrien-(1.3.6) und Cyclooctatrien-(1.3.5) journal February 1964
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Bonding Trends Traversing the Tetravalent Actinide Series: Synthesis, Structural, and Computational Analysis of An IV ( Ar acnac) 4 Complexes (An = Th, U, Np, Pu; Ar acnac = Ar N C(Ph)CHC(Ph) O ; Ar = 3,5- t Bu 2 C 6 H 3 ) journal July 2012
Electronic structure and spectra of uranocene journal March 1989
A Relativistic Study of the Electronic and Magnetic Properties of Cerocene and Thorocene and Its Anions journal April 2012
Ligand K-Edge X-ray Absorption Spectroscopy as a Probe of Ligand-Metal Bonding: Charge Donation and Covalency in Copper-Chloride Systems journal September 1994
Covalency in Americium(III) Hexachloride journal June 2017
Optimization of analysis of soft X-ray spectromicroscopy at the Ca 2p edge journal June 2009
Metal and Ligand K-Edge XAS of Organotitanium Complexes:  Metal 4p and 3d Contributions to Pre-edge Intensity and Their Contributions to Bonding journal January 2005
Electronic structure of nanoporous ceria from x-ray absorption spectroscopy and atomic multiplet calculations journal December 2007
Narrowing Due to Valence Mixing in the 3d Core Level Spectra for Ce Compounds journal July 1988
Chelation and stabilization of berkelium in oxidation state +IV journal April 2017
The nature of chemical bonding in actinide and lanthanide ferrocyanides determined by X-ray absorption spectroscopy and density functional theory journal January 2016
Bond Covalency and Oxidation State of Actinide Ions Complexed with Therapeutic Chelating Agent 3,4,3-LI(1,2-HOPO) journal April 2018
An Alkali Metal-Capped Cerium(IV) Imido Complex journal May 2016
Resonant inelastic x-ray scattering at the Ce L 3 edge of CePO 4 and CeO 2 : Implications for the valence of CeO 2 and related phenomena journal July 2005
Pentavalent Lanthanide Compounds: Formation and Characterization of Praseodymium(V) Oxides journal April 2016
Ab Initio Ligand-Field Theory Analysis and Covalency Trends in Actinide and Lanthanide Free Ions and Octahedral Complexes journal July 2017
Structures of organo-f-element compounds differing in the oxidation state of the central metal: crystal structures of bis([8]annulene) complexes of cerium(IV), ytterbium(III), and uranium(III) journal June 1991
Sulfur K-edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory of Dithiophosphinate Extractants: Minor Actinide Selectivity and Electronic Structure Correlations journal August 2012
Uncovering the Origin of Divergence in the CsM(CrO 4 ) 2 (M = La, Pr, Nd, Sm, Eu; Am) Family through Examination of the Chemical Bonding in a Molecular Cluster and by Band Structure Analysis journal January 2018
Emergence of the structure-directing role of f-orbital overlap-driven covalency journal February 2019
Influence of the Torsion Angle in 3,3′-Dimethyl-2,2′-bipyridine on the Intermediate Valence of Yb in (C 5 Me 5 ) 2 Yb(3,3′-Me 2 -bipy) journal September 2013
A computational investigation of orbital overlap versus energy degeneracy covalency in [UE 2 ] 2+ (E = O, S, Se, Te) complexes journal January 2020
New 7r-cyclooctate'I'raenyl and iT-cyclopentadienyl complexes of cerium journal July 1976
Lanthanide(III) complexes with cyclooctatetraene dianion. Synthetic chemistry, characterization, and physical properties journal December 1973
Orbital localization and delocalization effects in the U 5 f 2 configuration: Impurity problem journal May 1998
Effective core potential methods for the lanthanides journal April 1993
Pursuit of Record Breaking Energy Barriers: A Study of Magnetic Axiality in Diamide Ligated Dy III Single-Molecule Magnets journal January 2017
Does covalency really increase across the 5f series? A comparison of molecular orbital, natural population, spin and electron density analyses of AnCp 3 (An = Th–Cm; Cp = η 5 -C 5 H 5 ) journal January 2011
High resolution mapping of surface reduction in ceria nanoparticles journal January 2011
Segmented contraction scheme for small-core actinide pseudopotential basis sets journal March 2004
Elucidating bonding preferences in tetrakis(imido)uranate(VI) dianions journal April 2017
The electronic structure of actinide-containing molecules: a challenge to applied quantum chemistry journal July 1991
CORE-HOLE EFFECT IN THE Ce L 3 X-RAY ABSORPTION SPECTRA OF CeO 2 AND CeFe 2 : NEW EXAMINATION BY USING RESONANT X-RAY EMISSION SPECTROSCOPY journal June 2013
Ligand K-edge x-ray absorption spectroscopic studies: metal-ligand covalency in a series of transition metal tetrachlorides journal March 1995
Ligand K-edge X-ray absorption spectroscopy: covalency of ligand–metal bonds journal January 2005
Magnetic circular dichroism of UCl 6 in the ligand-to-metal charge-transfer spectral region journal January 2017