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Title: Synthesis and Utility of Neptunium(III) Hydrocarbyl Complex

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [1];  [1];  [2]; ORCiD logo [1]
  1. Univ. of Missouri, Columbia, MO (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
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To extend organoactinide chemistry beyond uranium, we report the first structurally characterized transuranic hydrocarbyl complex, Np[η4-Me2NC(H)C6H5]3, 1, from reaction of NpCl4(DME)2 with four equivalents of K[Me2NC(H)C6H5]. Unlike the U(III) species, the neptunium analogue can be used to access other Np(III) complexes. The reaction of 1 with three equivalents of HE2C(2,6-Mes2-C6H3), E = O, S, yields [(2,6-Mes2-C6H3)CE2]3Np(THF)2, maintaining the trivalent oxidation state.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Univ. of Missouri, Columbia, MO (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC02-05CH11231; SC0014174
OSTI ID:
1560610
Alternate ID(s):
OSTI ID: 1569498; OSTI ID: 1778221
Journal Information:
Angewandte Chemie (International Edition), Vol. 58, Issue 42; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

References (72)

[Am(C 5 Me 4 H) 3 ]: An Organometallic Americium Complex journal July 2019
Recent Developments in Synthesis and Structural Chemistry of Nonaqueous Actinide Complexes journal October 2012
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides journal September 1976
Magnetic Susceptibilities of Uranium (IV) Ions in Cubic Crystalline Fields journal September 1957
First example of a neutral homoleptic uranium alkyl. Synthesis, properties, and structure of U[CH(SiMe3)2]3 journal March 1989
Structural and Density Functional Studies of Uranium(III) and Lanthanum(III) Complexes with a Neutral Tripodal N-Donor Ligand Suggesting the Presence of a U−N Back-Bonding Interaction journal May 2002
Organometallic Neptunium Chemistry journal August 2017
Organometallic neptunium(III) complexes journal May 2016
Tris(.eta.5-cyclopentadienyl)alkyl and -alkenyl compounds of thorium(IV) journal February 1976
NN-diethyldithiocarbamate complexes of trivalent lanthanide and actinide elements and the crystal structure of tetraethylammonium neptunium(III) tetrakis-(NN-diethyldithiocarbamate) journal January 1970
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
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 Convenient Entry into Trivalent Actinide Chemistry: Synthesis and Characterization of AnI3(THF)4 and An[N(SiMe3)2]3 (An = U, Np, Pu) journal May 1994
Flexible coordination of the carboxylate ligand in tin(ii) amides and a 1,3-diaza-2,4-distannacyclobutanediyl journal January 2007
Functionalization of Carbon Dioxide and Carbon Disulfide Using a Stable Uranium(III) Alkyl Complex journal April 2011
Synthesis and Characterization of a Uranium(II) Monoarene Complex Supported by δ  Backbonding journal May 2014
A New Type of Organo-Iron Compound journal December 1951
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
Achievements in uranium alkyl chemistry: celebrating sixty years of synthetic pursuits journal January 2015
Observations on the thermal decomposition of some uranium(IV) tetraalkyls journal January 1974
Characterization of the anion [(.eta.5-C5H5)3 UIII-n-C4H9]-. Synthesis and crystal structure of tricyclopentadienyl n-butyluranium(III) lithium cryptate: [(C5H5)3UC4H9]-[LiC14H28N2O4]+ journal February 1986
Synthesis and Reactivity of Trivalent Tp*U(CH 2 Ph) 2 (THF): Insertion vs Oxidation at Low-Valent Uranium–Carbon Bonds journal January 2013
Olefin-Metathesis Catalysts for the Preparation of Molecules and Materials (Nobel Lecture) journal June 2006
Multiple Metal–Carbon Bonds for Catalytic Metathesis Reactions (Nobel Lecture) journal June 2006
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
Expanding the Family of Uranium(III) Alkyls: Synthesis and Characterization of Mixed-Ligand Derivatives: Expanding the Family of Uranium(III) Alkyls: Synthesis and Characterization of Mixed-Ligand Derivatives journal January 2016
Uranium-mediated activation of small molecules journal January 2011
Puzzling Lack of Temperature Dependence of the PuO 2 Magnetic Susceptibility Explained According to Ab Initio Wave Function Calculations journal January 2017
Synthesis of Heteroleptic Uranium (μ−η 6 :η 6 -C 6 H 6 ) 2− Sandwich Complexes via Facile Displacement of (η 5 -C 5 Me 5 ) 1− by Ligands of Lower Hapticity and Their Conversion to Heteroleptic Bis(imido) Compounds journal December 2009
Recent Advances in Organoactinide Chemistry As Exemplified by Cyclopentadienyl Compounds journal March 2013
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
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
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
Conversion of Americia to Anhydrous Trivalent Americium Halides journal January 2019
Susceptibilite magnetique de PuO2 journal June 1968
In Pursuit of Homoleptic Actinide Alkyl Complexes journal June 2012
L.—Action of carbon monoxide on nickel journal January 1890
Generation of Tp*2U(N3) from a family of new uranium(III) alkyl complexes journal February 2018
.sigma.-Alkyl and -aryl complexes of the group 4-7 transition metals journal April 1976
Electronic Structure and Photoelectron Spectroscopy of the Monomeric Uranium(III) Alkyl [η 5 -(CH 3 ) 5 C 5 ] 2 UCH[Si(CH 3 ) 3 ] 2 † , ‡ journal January 1996
Preparation of tetraalkyl phosphine complexes of the f-block metals. Crystal structure of Th(CH2Ph)4(Me2PCH2CH2PMe2) and U(CH2Ph)3Me(Me2PCH2CH2PMe2) journal February 1984
Advances in Transition Metal (Pd,Ni,Fe)-Catalyzed Cross-Coupling Reactions Using Alkyl-organometallics as Reaction Partners journal March 2011
Synthesis and characterization of NpCl 4 (DME) 2 and PuCl 4 (DME) 2 neutral transuranic An( iv ) starting materials journal January 2014
Non-aqueous neptunium and plutonium redox behaviour in THF – access to a rare Np( iii ) synthetic precursor journal January 2018
Use of Alkylsodium Reagents for the Synthesis of Trivalent Uranium Alkyl Complexes journal May 2012
A Homoleptic Uranium(III) Tris(aryl) Complex journal December 2016
The vitality of uranium molecular chemistry at the dawn of the XXIst century journal January 2006
Improving f-element single molecule magnets journal January 2015
Bioorganometallics: Future Trends in Drug Discovery, Analytical Chemistry, and Catalysis † , ‡ journal January 2011
Actinide organometallic complexes with π‐ligands journal August 2018
Metall-Kohlenstoff-Mehrfachbindungen in katalytischen Metathesereaktionen (Nobel-Vortrag) journal June 2006
Uranium( iii ) and thorium( iv ) alkyl complexes as potential starting materials journal January 2016
Energy Levels of U 4+ in an Octahedral Crystalline Field journal January 1965
Olefinmetathesekatalysatoren zur Synthese von Molekülen und Materialien (Nobel-Vortrag) journal June 2006
Stable uranium(IV) alkyl and aryl complexes journal September 1972
The Renaissance of Non-Aqueous Uranium Chemistry journal June 2015
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
Origin of Selectivity of a Triazinyl Ligand for Americium(III) over Neodymium(III) journal February 2019
Calculation of the Stevens factors α, β and γ in the intermediate coupling scheme for U and Np ions with f 2, f3 and f4 configurations journal January 1984
Synthesis and Reactivity of Homoleptic α-Metalated N,N -Dimethylbenzylamine Rare-Earth-Metal Complexes journal August 2011
Reduction chemistry of neptunium cyclopentadienide complexes: from structure to understanding journal January 2017
[Am(C 5 Me 4 H) 3 ]: An Organometallic Americium Complex journal July 2019
Structural Characterization of Pu[N(SiMe 3 ) 2 ] 3 , a Synthetically Useful Nonaqueous Plutonium(III) Precursor journal January 2008
Preparation, Solution Behavior, and Solid-State Structures of (1,3-R 2 C 5 H 3 ) 2 UX 2 , Where R Is CMe 3 or SiMe 3 and X Is a One-Electron Ligand journal March 1999
Mesitylcopper – A Powerful Tool in Synthetic Chemistry journal August 2012
Die Renaissance der nichtwässrigen Uranchemie journal June 2015
Lithium alkyl anions of uranium(IV) and uranium(V). Addition compounds of uranium(VI) hexaisopropoxide with lithium, magnesium, and aluminium alkyls journal January 1977
Pentamethylcyclopentadienyl organoactinides. Trivalent uranium organometallic chemistry and the unusual structure of bis(pentamethylcyclopentadienyl)uranium monochloride journal August 1979
Neglected neptunium journal October 2010
Synthesis and Characterization of a Uranium(II) Monoarene Complex Supported by δ  Backbonding journal May 2014
U(SMes*) n , ( n = 3, 4) and Ln(SMes*) 3 (Ln = La, Ce, Pr, Nd):  Lanthanide(III)/Actinide(III) Differentiation in Agostic Interactions and an Unprecedented η 3 Ligation Mode of the Arylthiolate Ligand, from X-ray Diffraction and DFT Analysis journal July 2006
The Vitality of Uranium Molecular Chemistry at the Dawn of the XXIst Century journal October 2006

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Enantiomerically Pure Tetravalent Neptunium Amidinates: Synthesis and Characterization journal June 2020
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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
actinides
neptunium
organometallics
oxidation
structure elucidation
neptunium
organometallic
hydrocarbyl
terphenyl