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Title: A Pseudotetrahedral Uranium(V) Complex

Journal Article · · Inorganic Chemistry
ORCiD logo [1];  [2]; ORCiD logo [1];  [3]; ORCiD logo [4]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. at Buffalo, NY (United States). Dept. of Chemistry
  3. Univ. of Rochester, NY (United States). Dept. of Chemistry
  4. Univ. at Buffalo, NY (United States). Dept. of Chemistry

A series of uranium amides were synthesized from N,N,N-cyclohexyl(trimethylsilyl)lithium amide [Li][N(TMS)Cy] and uranium tetrachloride to give U(NCySiMe3)x(Cl)4–x, where x = 2, 3, or 4. The diamide was then isolated as a bimetallic, bridging lithium chloride adduct ((UCl2(NCyTMS)2)2-LiCl(THF)2), and the tris(amide) was isolated as the lithium chloride adduct of the monometallic species (UCl(NCyTMS)3-LiCl(THF)2). The tetraamide complex was isolated as the four-coordinate pseudotetrahedron. Cyclic voltammetry revealed an easily accessible reversible oxidation wave, and upon chemical oxidation, the UV amido cation was isolated in near-quantitative yields. The synthesis of this family of compounds allows a direct comparison of the electronic structure and properties of isostructural UIV and UV tetraamide complexes. Spectroscopic investigations consisting of UV–vis, NIR, MCD, EPR, and U L3-edge XANES, along with density functional and wave function calculations, of the four-coordinate UIV and UV complexes have been used to understand the electronic structure of these pseudotetrahedral complexes.

Research Organization:
Los Alamos National Laboratory (LANL)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC52-06NA25396; SC0016002; SC0001136; AC02-76SF00515
OSTI ID:
1460655
Report Number(s):
LA-UR-18-21979
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 14 Vol. 57; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (73)

Organometallic Uranium(V)−Imido Halide Complexes: From Synthesis to Electronic Structure and Bonding journal April 2008
Pentavalent uranyl complexes journal August 2009
Main Group Atoms and Dimers Studied with a New Relativistic ANO Basis Set December 2003
The Renaissance of Non-Aqueous Uranium Chemistry journal June 2015
Small molecule activation at uranium coordination complexes: control of reactivity via molecular architecture journal January 2006
Uranium−Nitrogen Multiple Bonding: The Case of a Four-Coordinate Uranium(VI) Nitridoborate Complex journal April 2009
Synthesis, Characterization, and Multielectron Reduction Chemistry of Uranium Supported by Redox-Active α-Diimine Ligands journal October 2011
A photoelectron study of pentavalent uranium imido complexes journal December 1987
Cerium(III) and Uranium(IV) Complexes of the 2-Fluorophenyl Trimethylsilyl Amide Ligand: C–F → Ln/An Interactions that Modulate the Coordination Spheres of f-Block Elements journal May 2016
The Inverse Trans Influence in a Family of Pentavalent Uranium Complexes journal June 2014
Polarization Dependent High Energy Resolution X-ray Absorption Study of Dicesium Uranyl Tetrachloride journal December 2014
Tetrakis(bis(trimethylsilyl)amido)uranium(IV): Synthesis and Reactivity journal June 2013
Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table : Molcas 8 journal November 2015
EPR and Angle-Selected ENDOR Study of 5f-Ligand Interactions in the [U(η 7 -C 7 H 7 ) 2 ] - Anion, an f 1 Analogue of Uranocene journal June 1998
Probing the 5f Orbital Contribution to the Bonding in a U(V) Ketimide Complex journal February 2012
Organic Compounds of Uranium. II. Uranium(IV) Amides, Alkoxides and Mercaptides journal September 1956
SHELXT – Integrated space-group and crystal-structure determination journal January 2015
Orbitals for Analyzing Bonding and Magnetism of Heavy-Metal Complexes journal September 2015
Recent Developments in Synthesis and Structural Chemistry of Nonaqueous Actinide Complexes journal October 2012
A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach journal May 1980
Oxidation State Delineation via U L III -Edge XANES in a Series of Isostructural Uranium Coordination Complexes journal April 2012
A Weak Interaction between Iron and Uranium in Uranium Alkyl Complexes Supported by Ferrocene Diamide Ligands journal March 2008
Thorium(IV) and uranium(IV) carbamates journal April 1974
Comparative Study of f-Element Electronic Structure across a Series of Multimetallic Actinide and Lanthanoid-Actinide Complexes Possessing Redox-Active Bridging Ligands journal February 2010
Modified valence indices from the two-particle density matrix journal August 1994
New relativistic ANO basis sets for actinide atoms journal June 2005
Optimized Slater-type basis sets for the elements 1-118 journal May 2003
Fluorinated diarylamide complexes of uranium( iii , iv ) incorporating ancillary fluorine-to-uranium dative interactions journal January 2013
OLEX2 : a complete structure solution, refinement and analysis program journal January 2009
Influence of the Nature of the Ligands on the Electronic Ground State of Organouranium(V) Compounds, Studied by Electron Paramagnetic Resonance journal December 1997
Redox Processes in a Uranium Bis(1,1‘-diamidoferrocene) Complex journal May 2007
Crystal structure of tetrakis[bis(N,N'-dimethylethylenediamido)uranium(IV)], tetrameric globular complex journal August 1977
Steric control of redox events in organo-uranium chemistry: synthesis and characterisation of U( v ) oxo and nitrido complexes journal January 2016
Investigations of the Electronic Structure of Arene-Bridged Diuranium Complexes journal January 2013
An Alternative Approach to the g-Matrix: Theory and Applications journal June 2006
Molecular Structure and Electrochemical Behavior of Uranyl(VI) Complex with Pentadentate Schiff Base Ligand: Prevention of Uranyl(V) Cation−Cation Interaction by Fully Chelating Equatorial Coordination Sites journal March 2010
Examining the Effects of Ligand Variation on the Electronic Structure of Uranium Bis(imido) Species journal October 2016
Chemistry of uranium (V) journal October 1969
Ab initio calculation of anisotropic magnetic properties of complexes. I. Unique definition of pseudospin Hamiltonians and their derivation journal August 2012
Electrochemical and Spectroscopic Evidence on the One-Electron Reduction of U(VI) to U(V) on Magnetite journal April 2015
Synthesis, Structure, and Bonding of Stable Complexes of Pentavalent Uranyl journal December 2009
Bis[ N , N ′-bis(trimethylsilyl)ferrocene-1,1′-diaminato]uranium(IV) journal August 2006
IR Spectroelectrochemical Study on U V O 2 + Complex:  First Evidence for Weakening of UO Bond Strength in Uranyl Moiety with Reduction from U(VI) to U(V) journal May 2003
Oxo ligand functionalization in the uranyl ion (UO22+) journal February 2010
Tris((hexamethyldisilyl)amido)uranium(III): preparation and coordination chemistry journal June 1979
Tris[bis(trimethylsilyl)amido](trimethylsilylimido)uranium(V) journal September 1988
A short history of SHELX journal December 2007
The generalized Douglas–Kroll transformation journal November 2002
Chemistry with ADF journal January 2001
Recent Advances in Organoactinide Chemistry As Exemplified by Cyclopentadienyl Compounds journal March 2013
Carbon Dioxide Activation with Sterically Pressured Mid- and High-Valent Uranium Complexes journal September 2008
Calculation of EPR g Tensors for Transition-Metal Complexes Based on Multiconfigurational Perturbation Theory (CASPT2) journal August 2007
Investigation of the Electronic Ground States for a Reduced Pyridine(diimine) Uranium Series: Evidence for a Ligand Tetraanion Stabilized by a Uranium Dimer journal April 2015
Conductor-like Screening Model for Real Solvents: A New Approach to the Quantitative Calculation of Solvation Phenomena journal February 1995
Pentavalent uranium chemistry—synthetic pursuit of a rare oxidation state journal January 2009
Selective oxidants for organometallic compounds containing a stabilising anion of highly reactive cations: (3,5(CF3)2C6H3)4B−)Cp2Fe+ and (3,5(CF3)2C6H3)4B−)Cp*2Fe+ journal April 2000
Theoretical Description of the Structure and Magnetic Properties of Nitroxide−Cu(II)−Nitroxide Spin Triads by Means of Multiconfigurational Ab Initio Calculations journal May 2009
Molecular and Electronic Structures of Eight-Coordinate Uranium Bipyridine Complexes: A Rare Example of a Bipy 2– Ligand Coordinated to a U 4+ Ion journal February 2017
Synthesis and Structural Characterization of Magnesium Amide Complexes Containing −N[(R)(SiMe 3 )] Ligands journal February 2005
Actinide—amide complexes journal October 1974
Crystal structure and optical and magnetic properties of tetrakis(diethylamido)uranium(IV), a five-coordinate dimeric complex in the solid state journal October 1976
Uranium Hexakisamido Complexes journal September 2000
Generalized Gradient Approximation Made Simple journal October 1996
The restricted active space (RAS) state interaction approach with spin–orbit coupling journal May 2002
The Nature of the UC Double Bond: Pushing the Stability of High-Oxidation-State Uranium Carbenes to the Limit journal April 2013
Syntheses and crystal structures of tetrakis(diphenylamido)uranium(IV) and bis(.mu.-oxo-tris(diphenylamido)uranium(IV) lithium diethyl etherate) journal May 1977
New UIII and UIV silylamides and an improved synthesis of NaN(SiMe2R)2 (R = Me, Ph) journal December 2010
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT journal June 2005
Anomalous One-Electron Processes in the Chemistry of Uranium Nitrogen Multiple Bonds journal August 2014
Magnetic Properties and Electronic Structure of Neptunyl(VI) Complexes: Wavefunctions, Orbitals, and Crystal-Field Models journal May 2014
Relativistic regular two‐component Hamiltonians journal September 1993
Covalency effects on the ligand field splittings of octahedral 5f7 compounds journal March 1974
Convenient Synthesis, Structure, and Reactivity of (C 5 Me 5 )U(CH 2 C 6 H 5 ) 3 :  A Simple Strategy for the Preparation of Monopentamethylcyclopentadienyl Uranium(IV) Complexes journal December 2002

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