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
 

Elemental chalcogen reactions of a tetravalent uranium imidophosphorane complex: cleavage of dioxygen

Journal Article · · ChemComm
DOI:https://doi.org/10.1039/d2cc05066h· OSTI ID:2421236
 [1];  [2];  [3];  [3];  [3];  [2];  [3]
  1. Georgia Institute of Technology, Atlanta, GA (United States); OSTI
  2. Institut National des Sciences Appliquees, Toulouse (France). Laboratoire de Physique et Chimie des Nano-objets
  3. Georgia Institute of Technology, Atlanta, GA (United States)
+ Show Author Affiliations

Herein we report the first example of a mononuclear uranium complex, [U4+(NP(pip)3)4] (1-U), that selectively reduces dioxygen to produce a terminal oxo complex, [U6+O(NP(pip)3)4] (2-U; [NP(pip)3]1- is tris(piperidinyl)imidophosphorane). Reactions between 1-U and the heavier elemental chalcogens, S8 or Se0, result in six-coordinate U(VI) complexes, [U6+(κ2-E3)(NP(pip)3)4] (E = S (3-U) or Se (4-U)).

Research Organization:
Georgia Institute of Technology, Atlanta, GA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
SC0019385
OSTI ID:
2421236
Alternate ID(s):
OSTI ID: 1897769
Journal Information:
ChemComm, Journal Name: ChemComm Journal Issue: 95 Vol. 58; ISSN CHCOFS; ISSN 1359-7345
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (42)

Controlled Deprotection and Reorganization of Uranyl Oxo Groups in a Binuclear Macrocyclic Environment journal November 2012
Synthesis, Characterization, and Reactivity of a Uranium(VI) Carbene Imido Oxo Complex journal May 2014
Facile Dinitrogen and Dioxygen Cleavage by a Uranium(III) Complex: Cooperativity Between the Non‐Innocent Ligand and the Uranium Center journal October 2020
Synthesis of Terminal Uranium(IV) Disulfido and Diselenido Compounds by Activation of Elemental Sulfur and Selenium journal October 2013
Small-Molecule Activation at Uranium(III) journal April 2013
The Chemistry of the Actinide and Transactinide Elements book January 2006
Raman spectra of negative molecular ions doped in alkali halide crystals journal October 1969
Phosphoraneiminato complexes of transition metals journal February 1999
Molecular actinide compounds with soft chalcogen ligands journal July 2016
Synthesis, Electrochemistry, and Reactivity of the Actinide Trisulfides [K(18-crown-6)][An(η3-S3)(NR2)3] (An = U, Th; R = SiMe3) journal September 2016
Homoleptic Imidophosphorane Stabilization of Tetravalent Cerium journal March 2019
Actinide Carbonte Complexes and Their Importance in Actinide Environmental Chemistry journal January 1995
Synthesis, Molecular and Electronic Structure of U V (O)[N(SiMe 3 ) 2 ] 3 journal January 2012
Uranium–Ligand Multiple Bonding in Uranyl Analogues, [L═U═L] n + , and the Inverse Trans Influence journal December 2012
Characterization of the trisulfur radical anion S3- in blue solutions of alkali polysulfides in hexamethylphosphoramide journal October 1972
Reversible Chalcogen-Atom Transfer to a Terminal Uranium Sulfide journal December 2014
Synthesis and structure of the first uranium(VI) organometallic complex journal December 1992
Synthesis and Properties of High-Valent Organouranium Complexes Containing Terminal Organoimido and Oxo Functional Groups. A New Class of Organo-f-Element Complexes journal September 1995
Synthesis and Structure of a Stable Pentavalent-Uranyl Coordination Polymer journal June 2006
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
Stable Uranium(VI) Methyl and Acetylide Complexes and the Elucidation of an Inverse Trans Influence Ligand Series journal August 2013
Two-Electron Oxidative Atom Transfer at a Homoleptic, Tetravalent Uranium Complex journal April 2020
Actinide–Oxygen Multiple Bonds from Air: Synthesis and Characterization of a Thorium Oxo Supported by Redox-Active Ligands journal September 2022
CO 2 and CO/H 2 Conversion to Methoxide by a Uranium(IV) Hydride journal April 2019
Design, Isolation, and Spectroscopic Analysis of a Tetravalent Terbium Complex journal July 2019
Electronic Structure and Bonding in Actinyl Ions and their Analogs journal May 2007
Chalcogen Atom Transfer to Uranium(III): Synthesis and Characterization of [(R 2 N) 3 U] 2 (μ-E) and [(R 2 N) 3 U] 2 (μ-η 2 :η 2 -S 2 ) (R = SiMe 3 ; E = S, Se, Te) journal November 2012
Ubiquitous trisulphur radical ion S3−· journal November 1974
Towards uranium catalysts journal September 2008
Metallacyclic actinide catalysts for dinitrogen conversion to ammonia and secondary amines journal May 2020
Metal–ligand multiple bonding in uranium: structure and reactivity journal January 2010
Two-electron versus one-electron reduction of chalcogens by uranium( iii ): synthesis of a terminal U( v ) persulfide complex journal January 2014
Reactivity of uranium( iv ) bridged chalcogenido complexes U IV –E–U IV (E = S, Se) with elemental sulfur and selenium: synthesis of polychalcogenido-bridged uranium complexes journal January 2014
A sulphur and uranium fiesta! Synthesis, structure, and characterization of neutral terminal uranium( vi ) monosulphide, uranium( vi ) η 2 -disulphide, and uranium( iv ) phosphine sulphide complexes journal January 2019
Coinage metal tris(dialkylamido)imidophosphorane complexes as transmetallation reagents for cerium complexes journal January 2020
Chalcogen-atom abstraction reactions of a Di-iron imidophosphorane complex journal January 2021
Spectroscopic and electrochemical characterization of a Pr4+ imidophosphorane complex and the redox chemistry of Nd3+ and Dy3+ complexes journal January 2022
Synthesis and some reactions of tris(cyclopentadienyl)-uranium( IV ) hydrides; crystal structure of [U(C 5 H 4 Bu t ) 3 H] journal January 1992
Enhancing the reactivity of uranium(vi) organoimido complexes with diazoalkanesElectronic supplementary information (ESI) available: experimental, including general procedures, materials and synthesis of complexes 2 and 3. See http://www.rsc.org/suppdata/cc/b1/b109455f/ journal December 2001
Uranium-mediated activation of small molecules journal January 2011
Magnetic communication and reactivity of a stable homometallic cation–cation trimer of pentavalent uranyl journal January 2012

Similar Records

Coinage metal tris(dialkylamido)imidophosphorane complexes as transmetallation reagents for cerium complexes
Journal Article · Wed Apr 01 00:00:00 EDT 2020 · Dalton Transactions · OSTI ID:1803769
Divergent Stabilities of Tetravalent Cerium, Uranium, and Neptunium Imidophosphorane Complexes**
Journal Article · Thu Jul 13 00:00:00 EDT 2023 · Angewandte Chemie · OSTI ID:1994887

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
Chemistry