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Title: Reduction of CO2 and CS2 with Uranium(III) Metallocene Aryloxides

Journal Article · · Organometallics
 [1]; ORCiD logo [1]; ORCiD logo [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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Herein, the reactivity of two metallocene aryloxide U(III) complexes, [(C5Me5)2U(O-Ar)], Ar = 4-tBuC6H4, 1; Ar = 2,6-tBu2-4-CH3C6H2(BHT), 3, with CO2 and CS2 has been investigated. The reaction of 1 with CO2 produces a bridging oxo complex, [{(C5Me5)2(4-tBuC6H4-O)U}2(μ2-O)], 4, while 3 with CO2 results in reductive disproportionation to form the bridging carbonate species, [{(C5Me5)2(BHT)U}2(μ2-κ2:η1-CO3)], 5. The difference in reactivity can be attributed to the steric properties of the ligand because the reaction of 3 with an oxo-delivering agent yields a U(V) terminal oxo complex, [(C5Me5)2(BHT)U=O], 6. Reduction of CS2 to form a bridging (CS2)2- ligand, [{(C5Me5)2(tBuC6H4-O)U}2(μ2-CS2)], 7, is observed with 1, while the reaction of 3 with CS2 also produces a bridging (CS2)2- reduced ligand complex, followed by C-H bond activation of a methyl group from one (C5Me5)1- ring, [(C5Me5)2(BHT)U{μ2-C(H)S2}U(C5Me4CH2)(C5Me5)(BHT)], 8. All compounds are characterized by NMR and IR spectroscopy, and their solid-state structures are determined by X-ray crystallography.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC02-05CH11231; SC0021273
OSTI ID:
1960402
Journal Information:
Organometallics, Vol. 41, Issue 12; ISSN 0276-7333
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (56)

Carbon oxygenate transformations by actinide compounds and catalysts journal January 2017
Siloxides as Supporting Ligands in Uranium(III)-Mediated Small-Molecule Activation journal November 2012
Early actinide alkoxide chemistry. Synthesis, characterization, and molecular structures of thorium(IV) and uranium(IV) aryloxide complexes journal December 1992
Two-electron reductive reactivity of trivalent uranium tetraphenylborate complexes of (C5Me5)1− and (C5Me4H)1− journal August 2007
Synthesis and Characterization of Three Homoleptic Alkoxides of Uranium: [Li(THF)] 2 [U IV (O t Bu) 6 ], [Li(Et 2 O)][U V (O t Bu) 6 ], and U VI (O t Bu) 6 journal June 2008
Isolation of a [Fe(CO)4]2–-Bridged Diuranium Complex Obtained via Reduction of Fe(CO)5 with Uranium(III) journal May 2021
CC Bond Formation through Reductive Coupling of CS2 to Yield Uranium Tetrathiooxalate and Ethylenetetrathiolate Complexes journal May 2011
Small Molecule Activation by Uranium Tris(aryloxides): Experimental and Computational Studies of Binding of N 2 , Coupling of CO, and Deoxygenation Insertion of CO 2 under Ambient Conditions journal June 2011
Activation of SO 2 and CO 2 by Trivalent Uranium Leading to Sulfite/Dithionite and Carbonate/Oxalate Complexes journal August 2014
Formation of a Uranium Trithiocarbonate Complex via the Nucleophilic Addition of a Sulfide-Bridged Uranium Complex to CS 2 journal December 2011
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
Synthesis and structure of high-valent organouranium complexes containing terminal monooxo functional groups journal October 1993
Functionalization of Carbon Dioxide and Carbon Disulfide Using a Stable Uranium(III) Alkyl Complex journal April 2011
Formation of Trivalent U–C, U–N, and U–S Bonds and Their Reactivity toward Carbon Dioxide and Acetone journal November 2011
Carbon Dioxide Activation by a Uranium(III) Complex Derived from a Chelating Bis(aryloxide) Ligand journal May 2017
Reactivity of U–E–U (E = S, Se) Toward CO2, CS2, and COS: New Mixed-Carbonate Complexes of the Types U–CO2E–U (E = S, Se), U–CS2E–U (E = O, Se), and U–COSSe–U journal September 2012
Carbonate Formation from CO 2 via Oxo versus Oxalate Pathway: Theoretical Investigations into the Mechanism of Uranium-Mediated Carbonate Formation † journal November 2010
Carbon Dioxide Reduction and Carbon Monoxide Activation Employing a Reactive Uranium(III) Complex journal August 2005
Mono(pentamethylcyclopentadienyl)uranium(III) Complexes:  Synthesis, Properties, and X-ray Structures of (η-C 5 Me 5 )UI 2 (THF) 3 , (η-C 5 Me 5 )UI 2 (py) 3 , and (η-C 5 Me 5 )U[N(SiMe 3 ) 2 ] 2 journal February 2000
Uranium-mediated reductive conversion of CO2 to CO and carbonate in a single-vessel, closed synthetic cycle journal January 2012
A base-free terminal thorium phosphinidene metallocene and its reactivity toward selected organic molecules journal January 2019
Dithio- and Diselenophosphinate Thorium(IV) and Uranium(IV) Complexes: Molecular and Electronic Structures, Spectroscopy, and Transmetalation Reactivity journal December 2015
Lanthanide(II) Complexes Supported by N,O-Donor Tripodal Ligands: Synthesis, Structure, and Ligand-Dependent Redox Behavior journal August 2015
A Linear, O-Coordinated  1-CO2 Bound to Uranium journal September 2004
Chemistry of trivalent uranium metallocenes: electron-transfer reactions with carbon disulfide. Formation of [(RC5H4)3U]2[.mu.-.eta.1.eta.2-CS2] journal May 1986
Methane: a new frontier in organometallic chemistry journal January 2012
CO2 Activation with Formation of Uranium Carbonate Complexes in a Closed Synthetic Cycle journal January 2020
C–H Bond Activation by an Isolated Dinuclear U(III)/U(IV) Nitride journal January 2020
Insights into the mechanism of carbonate formation through reductive cleavage of carbon dioxide with low-valent uranium centers journal January 2010
Oxo-bridged bimetallic organouranium complexes: The crystal structure of μ-oxo-bis[tris(cyclopentadienyl)uranium(IV)] journal May 1996
Homogeneous iron complexes for the conversion of dinitrogen into ammonia and hydrazine journal January 2010
Synthesis of a Thorium Tuck-In Complex, [(η 5 :η 1 -C 5 Me 4 CH 2 )(η 5 -C 5 Me 5 )Th{ i PrNC(Me)N i Pr}], by CH Bond Activation Initiated by (C 5 Me 5 ) − journal October 2009
Multimetallic Cooperativity in Uranium-Mediated CO 2 Activation journal April 2014
Uranium Tris-aryloxide Derivatives Supported by Triazacyclononane:  Engendering a Reactive Uranium(III) Center with a Single Pocket for Reactivity journal April 2003
The role of uranium–arene bonding in H2O reduction catalysis journal December 2017
Reductive disproportionation of carbon dioxide to carbonate and squarate products using a mixed-sandwich U( iii ) complex journal January 2008
Actinide Metallocene Hydride Chemistry: C–H Activation in Tetramethylcyclopentadienyl Ligands to Form [μ-η 5 -C 5 Me 3 H(CH 2 )- κC ] 2– Tuck-over Ligands in a Tetrathorium Octahydride Complex journal October 2013
C–H Bond Addition across a Transient Uranium–Nitrido Moiety and Formation of a Parent Uranium Imido Complex journal July 2018
Uranium azide photolysis results in C–H bond activation and provides evidence for a terminal uranium nitride journal July 2010
Sterically encumbered mixed sandwich compounds of uranium(III): Synthesis and reactivity with small molecules journal February 2018
From Chemical Curiosities and Trophy Molecules to Uranium-Based Catalysis: Developments for Uranium Catalysis as a New Facet in Molecular Uranium Chemistry journal May 2021
Uranium Tetrakis-Aryloxide Derivatives Supported by Tetraazacyclododecane: Synthesis of Air-Stable, Coordinatively-Unsaturated U(IV) and U(V) Complexes journal November 2016
Carbon Disulfide (CS2) Mechanisms in Formation of Atmospheric Carbon Dioxide (CO2) Formation from Unconventional Shale Gas Extraction and Processing Operations and Global Climate Change journal January 2015
Carbon Dioxide Activation with Sterically Pressured Mid- and High-Valent Uranium Complexes journal September 2008
Bispentamethylcyclopentadienyl uranium(IV) thiolate compounds. Synthesis and reactions with CO2 and CS2 journal May 1999
Activation of Small Molecules by Molecular Uranium Complexes book April 2014
Coordination Chemistry and QTAIM Analysis of Homoleptic Dithiocarbamate Complexes, M(S 2 CN i Pr 2 ) 4 (M = Ti, Zr, Hf, Th, U, Np) journal August 2018
A Crystallizable f-Element Tuck-In Complex: The Tuck-in Tuck-over Uranium Metallocene [(C 5 Me 5 )U{μ-η 5 :η 1 :η 1 -C 5 Me 3 (CH 2 ) 2 }(μ-H) 2 U(C 5 Me 5 ) 2 ] journal June 2008
Synthesis and Reduction of Heteroleptic Bis(cyclopentadienyl) Uranium(III) Complexes journal May 2022
Organometallic Uranium(V)−Imido Halide Complexes: From Synthesis to Electronic Structure and Bonding journal April 2008
Uranium complexes with amide, alkoxide and thiolate ligands journal October 1994
Synthesis of (C 5 Me 5 ) 2 (C 5 Me 4 H)UMe, (C 5 Me 5 ) 2 (C 5 H 5 )UMe, and (C 5 Me 5 ) 2 UMe[CH(SiMe 3 ) 2 ] from Cationic Metallocenes for the Evaluation of Sterically Induced Reduction journal November 2008
Synthesis and properties of bis(pentamethylcyclopentadienyl) actinide hydrocarbyls and hydrides. A new class of highly reactive f-element organometallic compounds journal November 1981
Formation of (C 5 Me 5 ) 2 U(EPh)Me, (C 5 Me 5 ) 2 U(EPh) 2 , and (C 5 Me 5 ) 2 U( η 2 -TeC 6 H 4 ) from (C 5 Me 5 ) 2 UMe 2 and PhEEPh (E = S, Se, Te) journal August 2007
CO, CO2 and CS2 activation by divalent ytterbium hydrido complexes journal January 2022
Thorium(IV) and Uranium(IV) Ketimide Complexes Prepared by Nitrile Insertion into Actinide−Alkyl and −Aryl Bonds journal September 2004

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Aromatic compounds
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Ligands
Oxides
Reactivity