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Title: Trends in Covalency for d- and f-Element Metallocene Dichlorides Identified Using Chlorine K-Edge X-Ray Absorption Spectroscopy and Time Dependent-Density Functional Theory

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/ja9015759· OSTI ID:956564
 [1]
  1. Los Alamos National Laboratory
+ Show Author Affiliations

Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE
DOE Contract Number:
AC52-06NA25396
OSTI ID:
956564
Report Number(s):
LA-UR-09-01192; LA-UR-09-1192
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society
Country of Publication:
United States
Language:
English

References (76)

Spectrum analysis of U 3+ :LaCl 3 journal May 1980
Possible F-Shell Covalency in the Actinide Elements journal April 1950
Possible f-Shell Covalency in the Actinide Elements journal October 1950
The Separation of Americium and Curium from the Rare Earth Elements journal June 1950
The structure and bonding of 4$f$ and 5$f$ series organometallic compounds book January 1976
Structural criteria for the mode of bonding of organoactinides and -lanthanides and related compounds journal August 1980
Characterization of Actinide Bonding in Th(S 2 PMe 2 ) 4 by Synchrotron X-ray Diffraction journal September 1998
Covalency in f-element bonds journal October 2002
Covalency in the actinide dioxides: Systematic study of the electronic properties using screened hybrid density functional theory journal July 2007
Uranium and Lanthanide Complexes with the 2-Mercapto Benzothiazolate Ligand: Evidence for a Specific Covalent Binding Site in the Differentiation of Isostructural Lanthanide(III) and Actinide(III) Compounds journal December 2007
Covalency in the f Element−Chalcogen Bond. Computational Studies of M[N(EPR 2 ) 2 ] 3 (M = La, Ce, Pr, Pm, Eu, U, Np, Pu, Am, Cm; E = O, S, Se, Te; R = H, i Pr, Ph) journal September 2008
Experimental and Theoretical Comparison of Actinide and Lanthanide Bonding in M[N(EPR 2 ) 2 ] 3 Complexes (M = U, Pu, La, Ce; E = S, Se, Te; R = Ph, i Pr, H) journal January 2008
An x-ray photoelectron spectroscopic study of uranium compounds journal May 1986
Cyclopentadienyl—Actinide Complexes: Bonding and Electronic Structure journal September 1991
Covalency in the uranyl ion: A polarized x-ray spectroscopic study journal November 2002
On the inverse trans influence. Density functional studies of [MOX5]n– (M = Pa, n = 2; M = U, n = 1; M = Np, n = 0; X = F, Cl or Br) journal February 2002
Titanocene as an intermediate in reactions involving molecular hydrogen and nitrogen journal February 1972
Solution structure and dynamics of binuclear dinitrogen complexes of bis(pentamethylcyclopentadienyl)titanium(II) and bis(pentamethylcyclopentadienyl)zirconium(II) journal May 1978
Halide, hydride, alkyl, and dinitrogen complexes of bis(pentamethylcyclopentadienyl)hafnium journal January 1985
Pentamethylcyclopentadienyl organoactinides. Trivalent uranium organometallic chemistry and the unusual structure of bis(pentamethylcyclopentadienyl)uranium monochloride journal August 1979
Synthesis and properties of bis(pentamethylcyclopentadienyl) actinide hydrocarbyls and hydrides. A new class of highly reactive f-element organometallic compounds journal November 1981
Koordinative komplexe des antibasen—basen-systems urantetrachlorid und tricyclopentadienyluran(IV)-chlorid journal February 1974
The nature of bis(cyclopentadienyl)uranium dichloride and cyclopentadienyluranium trichloride in solution and in the solid state journal May 1979
Effect of the Nature of Metallocene Complexes of Group IV Metals on Their Performance in Catalytic Ethylene and Propylene Polymerization journal April 2000
Group 4 metallocene polymerisation catalysts: quantification of ring substituent steric effects journal January 2006
Expanding the chemistry of U3+ reducing agents journal April 2006
Metallocene and related catalysts for olefin, alkyne and silane dimerization and oligomerization journal January 2006
Strained Metallocenophanes and Related Organometallic Rings Containing π‐Hydrocarbon Ligands and Transition‐Metal Centers journal June 2007
Reagent-Controlled Transition-Metal-Catalyzed Radical Reactions journal August 2000
Titanocene(III)-Promoted Reformatsky Additions journal September 2003
Non-platinum group metal antitumor agents. History, current status, and perspectives journal October 1987
Metallocenes in biochemistry, microbiology & medicine journal March 1986
X-ray absorption edge spectroscopy of ligands bound to open-shell metal ions: chlorine K-edge studies of covalency in tetrachlorocuprate(2-) journal February 1990
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
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:  A Direct Probe of Ligand−Metal Covalency journal December 2000
S K-Edge X-ray Absorption Spectroscopic Investigation of the Ni-Containing Superoxide Dismutase Active Site:  New Structural Insight into the Mechanism journal February 2004
Ligand K-edge X-ray absorption spectroscopy: covalency of ligand–metal bonds journal January 2005
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
Metal and Ligand K-edge XAS of Titanium−TEMPO Complexes:  Determination of Oxidation States and Insights into Ti−O Bond Homolysis journal May 2006
X-ray absorption methods for the determination of Ru–Cl bond covalency in olefin metathesis catalysts: On the normalization of chlorine K-edges in ruthenium complexes journal June 2006
Description of the Ground-State Covalencies of the Bis(dithiolato) Transition-Metal Complexes from X-ray Absorption Spectroscopy and Time-Dependent Density-Functional Calculations journal March 2007
Covalency Trends in Group IV Metallocene Dichlorides. Chlorine K-Edge X-Ray Absorption Spectroscopy and Time Dependent-Density Functional Theory journal June 2008
Probing the Electronic Structures of [Cu 2 (μ-XR 2 )] n + Diamond Cores as a Function of the Bridging X Atom (X = N or P) and Charge ( n = 0, 1, 2) journal March 2008
Structural, Spectroscopic, and Theoretical Elucidation of a Redox-Active Pincer-Type Ancillary Applied in Catalysis journal March 2008
Nonparameterized molecular orbital calculations and photoelectron spectroscopy of open- and closed-shell M(IV) M(.eta.5-C5H5)2L2 complexes journal October 1975
Structure and chemistry of bis(cyclopentadienyl)-MLn complexes journal March 1976
Valence electronic structures of the organouranium dicyclopentadienyl complexes (.eta.5-C5H5)2UX2 (X = chlorine or methyl) journal October 1983
Electronic structures of the (.eta.5-C5H5)2TiL2 complexes (L = fluorine, chlorine, bromine, iodine, and methyl) journal February 1984
Carbon monoxide activation by biscyclopentadienyl complexes of Group 4 metals and actinides: .eta.2-acyl complexes journal July 1985
The quasi-relativistic Xα-SW molecular orbital method in organo-f-element chemistry: applications to UCl4, (η5-C5H5)4U and (η5-C5H5)2UCl2 journal September 1985
Actinide-to-carbon bonds in actinide bis(cyclopentadienyl)dialkyl, -butadiene, -metallacyclopentadiene, and -cyclobutadiene complexes journal May 1987
The electronic structure of actinide-containing molecules: a challenge to applied quantum chemistry journal July 1991
Bent metallocenes revisited journal January 1998
The Electronic Influence of Ring Substituents and Ansa Bridges in Zirconocene Complexes as Probed by Infrared Spectroscopic, Electrochemical, and Computational Studies journal August 2002
A study on the excitations of ligand-to-metal charge transfer in complexes Cp2MCl2 (Cp=π-C5H5, M=Ti, Zr, Hf) by density functional theory journal July 2003
Spin−Orbit Relativistic Time-Dependent Density Functional Calculations of the Metal and Ligand Pre-Edge XAS Intensities of Organotitanium Complexes:  TiCl 4 , Ti(η 5 -C 5 H 5 )Cl 3 , and Ti(η 5 -C 5 H 5 ) 2 Cl 2 journal June 2007
The electronic structure and photoelectron spectra of dichlorodi-π-cyclopentadienyl-titanium(IV),-zirconium(IV) and -hafnium(IV) journal March 1975
He(I)- AND He(II)- Excited photoelectron spectra of bis (pentamethylcyclopentadienyl) zirconiumdichloride journal January 1980
Photoelectron spectroscopy of f-element organometallic complexes. 4. Comparative studies of bis(pentamethylcyclopentadienyl) dichloride and dimethyl complexes of uranium(IV), thorium(IV), and zirconium(IV) journal August 1981
Absolute Metal−Ligand σ Bond Enthalpies in Group 4 Metallocenes. A Thermochemical, Structural, Photoelectron Spectroscopic, and ab Initio Quantum Chemical Investigation journal January 1999
Spectroscopic and theoretical studies of the unusual EPR parameters of distorted tetrahedral cupric sites: correlations to x-ray spectral features of core levels journal April 1987
Variable photon energy photoelectron spectroscopic studies of copper chlorides: an experimental probe of metal-ligand bonding and changes in electronic structure on ionization journal January 1988
Relationship between the Dipole Strength of Ligand Pre-Edge Transitions and Metal−Ligand Covalency journal October 1999
The Crystal Structure of Cesium Chlorocuprate, Cs 2 CuCl 4 , and the Spectrum of the Chlorocuprate Ion journal March 1952
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide journal May 1994
Electronic Structure, Excited States, and Photoelectron Spectra of Uranium, Thorium, and Zirconium Bis(Ketimido) Complexes (C 5 R 5 ) 2 M[−NCPh 2 ] 2 (M = Th, U, Zr; R = H, CH 3 ) journal June 2005
Theoretical Investigation of C−H/Olefin Coupling Catalyzed by Zirconium(IV) Complexes journal September 2004
Density Functional Theory Investigations of the Forbidden Double Insertion of Diazomethane into Zr−C Bonds of Cp2Zr(CH3)2 journal August 2007
Geometry prediction of hafnocenes by quantum chemical methods journal July 2007
Organometallic Uranium(V)−Imido Halide Complexes: From Synthesis to Electronic Structure and Bonding journal April 2008
Chemical Speciation of the Uranyl Ion under Highly Alkaline Conditions. Synthesis, Structures, and Oxo Ligand Exchange Dynamics journal April 1999
Local Structure and Charge Distribution in the UO 2 −U 4 O 9 System journal November 2004
Bonding in tris(.eta.5-cyclopentadienyl) actinide complexes. 5. A comparison of the bonding in neptunium, plutonium, and transplutonium compounds with that in lanthanide compounds and a transition-metal analog journal January 1991
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

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY