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Title: Reduction of Carbonyl Groups by Uranium(III) and Formation of a Stable Amide Radical Anion

Abstract

In this work, methyl benzoate, N,N-dimethylbenzamide, and benzophenone were reduced by UIII[N(SiMe3)2]3 resulting in uranium(IV) products. Reduction of benzophenone lead to UIV[OCPh2)][N(SiMe3)2]3, (1.1) which forms the dinuclear complex, [N(SiMe3)2]3UIV(OCPhPh-CPh2O)UIV[N(SiMe3)2]3 (1.2), through coupling of the ketyl radical species upon crystallization. Reaction of N,N-dimethylbenzamide with UIII[N(SiMe3)2]3 resulted in UIV[OC(Ph)(NMe2)][N(SiMe3)2]3 (2), a uranium(IV) compound and the first example of a charge-separated amide radical. In the case of methyl benzoate, the reduction resulted in UIV(OMe)[N(SiMe3)2]3 (3) and benzaldehyde as the reduced organic fragment. Compound 2 showed the ability to act as a uranium(III) synthon in its reactivity with trimethylsilyl azide, a reaction that yielded UV(=NSiMe3)[N(SiMe3)2]3. Additionally, 2 was reduced with potassium graphite resulting in [U(μ-O)[O=C(NMe2)(Ph)][N(SiMe3)2]2]2 (4), a dinuclear uranium compound bridged by oxo ligands. Reduction of 2 in the presence of 15-crown-5 afforded isolation of the mono-oxo compound, [(15-crown-5)2K][UO[N(SiMe3)2]3] (5). Lastly, the results expand the reduction capabilities of UIII complexes and demonstrate a strategy for isolating novel metal-stabilized radicals.

Authors:
 [1]; ORCiD logo [1];  [2];  [1];  [1]; ORCiD logo [1]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
  2. Univ. of Pennsylvania, Philadelphia, PA (United States); Children's Hospital of Philadelphia, PA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Actinide Science & Technology (CAST)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1470214
Alternate Identifier(s):
OSTI ID: 1412572
Grant/Contract Number:  
SC0016568
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 24; Journal Issue: 4; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; EPR spectroscopy; radicals; reactive intermediates; redox chemistry; uranium

Citation Formats

Mullane, Kimberly C., Cheisson, Thibault, Nakamaru-Ogiso, Eiko, Manor, Brian C., Carroll, Patrick J., and Schelter, Eric J. Reduction of Carbonyl Groups by Uranium(III) and Formation of a Stable Amide Radical Anion. United States: N. p., 2017. Web. doi:10.1002/chem.201703396.
Mullane, Kimberly C., Cheisson, Thibault, Nakamaru-Ogiso, Eiko, Manor, Brian C., Carroll, Patrick J., & Schelter, Eric J. Reduction of Carbonyl Groups by Uranium(III) and Formation of a Stable Amide Radical Anion. United States. doi:10.1002/chem.201703396.
Mullane, Kimberly C., Cheisson, Thibault, Nakamaru-Ogiso, Eiko, Manor, Brian C., Carroll, Patrick J., and Schelter, Eric J. Tue . "Reduction of Carbonyl Groups by Uranium(III) and Formation of a Stable Amide Radical Anion". United States. doi:10.1002/chem.201703396. https://www.osti.gov/servlets/purl/1470214.
@article{osti_1470214,
title = {Reduction of Carbonyl Groups by Uranium(III) and Formation of a Stable Amide Radical Anion},
author = {Mullane, Kimberly C. and Cheisson, Thibault and Nakamaru-Ogiso, Eiko and Manor, Brian C. and Carroll, Patrick J. and Schelter, Eric J.},
abstractNote = {In this work, methyl benzoate, N,N-dimethylbenzamide, and benzophenone were reduced by UIII[N(SiMe3)2]3 resulting in uranium(IV) products. Reduction of benzophenone lead to UIV[OC∙Ph2)][N(SiMe3)2]3, (1.1) which forms the dinuclear complex, [N(SiMe3)2]3UIV(OCPhPh-CPh2O)UIV[N(SiMe3)2]3 (1.2), through coupling of the ketyl radical species upon crystallization. Reaction of N,N-dimethylbenzamide with UIII[N(SiMe3)2]3 resulted in UIV[OC∙(Ph)(NMe2)][N(SiMe3)2]3 (2), a uranium(IV) compound and the first example of a charge-separated amide radical. In the case of methyl benzoate, the reduction resulted in UIV(OMe)[N(SiMe3)2]3 (3) and benzaldehyde as the reduced organic fragment. Compound 2 showed the ability to act as a uranium(III) synthon in its reactivity with trimethylsilyl azide, a reaction that yielded UV(=NSiMe3)[N(SiMe3)2]3. Additionally, 2 was reduced with potassium graphite resulting in [U(μ-O)[O=C(NMe2)(Ph)][N(SiMe3)2]2]2 (4), a dinuclear uranium compound bridged by oxo ligands. Reduction of 2 in the presence of 15-crown-5 afforded isolation of the mono-oxo compound, [(15-crown-5)2K][UO[N(SiMe3)2]3] (5). Lastly, the results expand the reduction capabilities of UIII complexes and demonstrate a strategy for isolating novel metal-stabilized radicals.},
doi = {10.1002/chem.201703396},
journal = {Chemistry - A European Journal},
number = 4,
volume = 24,
place = {United States},
year = {2017},
month = {9}
}

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Works referenced in this record:

Charge-Separation in Uranium Diazomethane Complexes Leading to C−H Activation and Chemical Transformation
journal, March 2008

  • Lam, Oanh P.; Feng, Patrick L.; Heinemann, Frank W.
  • Journal of the American Chemical Society, Vol. 130, Issue 9
  • DOI: 10.1021/ja0766472

Isolation of a uranium( iii ) benzophenone ketyl radical that displays redox-active ligand behaviour
journal, January 2014

  • Matson, Ellen M.; Kiernicki, John J.; Anderson, Nickolas H.
  • Dalton Trans., Vol. 43, Issue 48
  • DOI: 10.1039/C4DT01636J

Tris((hexamethyldisilyl)amido)uranium(III): preparation and coordination chemistry
journal, June 1979


Enhancing the Value of Free Metals in the Synthesis of Lanthanoid Formamidinates: Is a Co-oxidant Needed?
journal, November 2015

  • Deacon, Glen B.; Junk, Peter C.; Werner, Daniel
  • Chemistry - A European Journal, Vol. 22, Issue 1
  • DOI: 10.1002/chem.201502953

Selective Reduction of Barbituric Acids Using SmI 2 /H 2 O: Synthesis, Reactivity, and Structural Analysis of Tetrahedral Adducts
journal, October 2013

  • Szostak, Michal; Sautier, Brice; Spain, Malcolm
  • Angewandte Chemie International Edition, Vol. 52, Issue 48
  • DOI: 10.1002/anie.201306484

Diamagnetic Corrections and Pascal's Constants
journal, April 2008

  • Bain, Gordon A.; Berry, John F.
  • Journal of Chemical Education, Vol. 85, Issue 4
  • DOI: 10.1021/ed085p532

Anomalous One-Electron Processes in the Chemistry of Uranium Nitrogen Multiple Bonds
journal, August 2014

  • Mullane, Kimberly C.; Lewis, Andrew J.; Yin, Haolin
  • Inorganic Chemistry, Vol. 53, Issue 17
  • DOI: 10.1021/ic501149u

Synthesis of a Nitrido-Substituted Analogue of the Uranyl Ion, [N═U═O] +
journal, May 2010

  • Fortier, Skye; Wu, Guang; Hayton, Trevor W.
  • Journal of the American Chemical Society, Vol. 132, Issue 20
  • DOI: 10.1021/ja101567h

NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist
journal, May 2010

  • Fulmer, Gregory R.; Miller, Alexander J. M.; Sherden, Nathaniel H.
  • Organometallics, Vol. 29, Issue 9
  • DOI: 10.1021/om100106e

A Catalytic System Consisting of Vanadium, Chlorosilane, and Aluminum Metal in the Stereoselective Pinacol Coupling Reaction of Benzaldehyde Derivatives
journal, October 1999

  • Hirao, Toshikazu; Hatano, Bunpei; Imamoto, Yuka
  • The Journal of Organic Chemistry, Vol. 64, Issue 20
  • DOI: 10.1021/jo990902m

Magnetic Susceptibility of Uranium Complexes
journal, August 2014

  • Kindra, Douglas R.; Evans, William J.
  • Chemical Reviews, Vol. 114, Issue 18
  • DOI: 10.1021/cr500242w

A Complete Family of Terminal Uranium Chalcogenides, [U(E)(N{SiMe 3 } 2 ) 3 ] (E = O, S, Se, Te)
journal, September 2012

  • Brown, Jessie L.; Fortier, Skye; Lewis, Richard A.
  • Journal of the American Chemical Society, Vol. 134, Issue 37
  • DOI: 10.1021/ja305712m

Polynuclear Cation−Cation Complexes of Pentavalent Uranyl: Relating Stability and Magnetic Properties to Structure
journal, December 2008

  • Nocton, Grégory; Horeglad, Pawel; Pécaut, Jacques
  • Journal of the American Chemical Society, Vol. 130, Issue 49
  • DOI: 10.1021/ja804766r

Redox reactions of dopamine transients in aqueous solution: a pulse radiolysis study
journal, January 1994

  • Maity, Dilip K.; Mohan, Hari; Mittal, Jai P.
  • Journal of the Chemical Society, Perkin Transactions 2, Issue 4
  • DOI: 10.1039/p29940000919

[2π+2π] Cycloaddition of Isocyanates to Uranium(IV) Imido Complexes for the Synthesis of U(IV) κ 2 -Ureato Compounds
journal, February 2017


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

  • Avens, Larry R.; Bott, Simon G.; Clark, David L.
  • Inorganic Chemistry, Vol. 33, Issue 10
  • DOI: 10.1021/ic00088a030

Reactivity of Bulky Formamidinatosamarium(II or III) Complexes with C═O and C═S Bonds
journal, November 2014

  • Deacon, Glen B.; Junk, Peter C.; Wang, Jun
  • Inorganic Chemistry, Vol. 53, Issue 23
  • DOI: 10.1021/ic502181g

Studies on the Mechanism, Selectivity, and Synthetic Utility of Lactone Reduction Using SmI 2 and H 2 O
journal, October 2009

  • Parmar, Dixit; Duffy, Lorna A.; Sadasivam, Dhandapani V.
  • Journal of the American Chemical Society, Vol. 131, Issue 42
  • DOI: 10.1021/ja906396u

Mechanism of SmI 2 /Amine/H 2 O-Promoted Chemoselective Reductions of Carboxylic Acid Derivatives (Esters, Acids, and Amides) to Alcohols
journal, October 2014

  • Szostak, Michal; Spain, Malcolm; Eberhart, Andrew J.
  • The Journal of Organic Chemistry, Vol. 79, Issue 24
  • DOI: 10.1021/jo5018525

Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide
journal, May 1994

  • Küchle, W.; Dolg, M.; Stoll, H.
  • The Journal of Chemical Physics, Vol. 100, Issue 10
  • DOI: 10.1063/1.466847

Allylsamarium Bromide-Mediated Cascade Cyclization of Homoallylic Esters. Synthesis of 2-(2-Hydroxyalkyl)cyclopropanols and 2-(2-Hydroxyethyl)bicyclo[2.1.1]hexan-1-ols
journal, December 2014

  • Shen, Mengmeng; Tu, Yawei; Xie, Guanqun
  • The Journal of Organic Chemistry, Vol. 80, Issue 1
  • DOI: 10.1021/jo501797w

Bis(pentamethylcyclopentadienyl) U(III) oxide and U(IV) oxide carbene complexes
journal, November 2004


Synthesis and Characterization of N-Heterocyclic Carbene Complexes of Uranium(III)
journal, February 2004

  • Nakai, Hidetaka; Hu, Xile; Zakharov, Lev N.
  • Inorganic Chemistry, Vol. 43, Issue 3
  • DOI: 10.1021/ic035142j

Harnessing redox activity for the formation of uranium tris(imido) compounds
journal, July 2014

  • Anderson, Nickolas H.; Odoh, Samuel O.; Yao, Yiyi
  • Nature Chemistry, Vol. 6, Issue 10
  • DOI: 10.1038/nchem.2009

Spectroscopic and Structural Elucidation of Uranium Dioxophenoxazine Complexes
journal, June 2015


Reversible Sigma C–C Bond Formation Between Phenanthroline Ligands Activated by (C 5 Me 5 ) 2 Yb
journal, June 2014

  • Nocton, Grégory; Lukens, Wayne W.; Booth, Corwin H.
  • Journal of the American Chemical Society, Vol. 136, Issue 24
  • DOI: 10.1021/ja502271q

Multielectron C–O Bond Activation Mediated by a Family of Reduced Uranium Complexes
journal, March 2014

  • Kiernicki, John J.; Newell, Brian S.; Matson, Ellen M.
  • Inorganic Chemistry, Vol. 53, Issue 7
  • DOI: 10.1021/ic500012x

Trivalent Cerium and Praseodymium Aromatic Ketone Adducts
journal, November 2012

  • Crozier, Alan R.; Törnroos, Karl W.; Maichle-Mössmer, Cäcilia
  • European Journal of Inorganic Chemistry, Vol. 2013, Issue 3
  • DOI: 10.1002/ejic.201201171

A Linear, O-Coordinated  1-CO2 Bound to Uranium
journal, September 2004


Carbon monoxide coupling and functionalisation at a simple uranium coordination complex
journal, January 2011

  • Arnold, Polly L.; Turner, Zoë R.; Bellabarba, Ronan M.
  • Chem. Sci., Vol. 2, Issue 1
  • DOI: 10.1039/C0SC00452A

Synthese und Struktur des ersten Samarium(II)-Komplexes mit σ-gebundenen Alkylliganden und dessen Reaktion mit Benzophenon
journal, December 1997


Nuclear magnetic resonance and chemical studies of uranium(V) alkoxides
journal, October 1983

  • Eller, P. Gary; Vergamini, P. J.
  • Inorganic Chemistry, Vol. 22, Issue 22
  • DOI: 10.1021/ic00164a005

Anhydrous Photochemical Uranyl(VI) Reduction:  Unprecedented Retention of Equatorial Coordination Accompanying Reversible Axial Oxo/Alkoxide Exchange
journal, November 2006

  • Kannan, Shanmugaperumal; Vaughn, Anthony E.; Weis, Eric M.
  • Journal of the American Chemical Society, Vol. 128, Issue 43
  • DOI: 10.1021/ja065822w

Elucidating the Mechanism of Uranium Mediated Diazene N═N Bond Cleavage
journal, November 2016


Estimating the Limiting Reducing Power of SmI 2 /H 2 O/Amine and YbI 2 /H 2 O/Amine by Efficient Reduction of Unsaturated Hydrocarbons
journal, February 2006

  • Dahlén, Anders; Nilsson, Åke; Hilmersson, Göran
  • The Journal of Organic Chemistry, Vol. 71, Issue 4
  • DOI: 10.1021/jo052268k

Transfer of Ketyls from Alkali Metals to Transition Metals. Formation and Diverse Reactivities of d-Block Transition-Metal Ketyls
journal, May 1999

  • Hou, Zhaomin; Fujita, Akira; Koizumi, Take-aki
  • Organometallics, Vol. 18, Issue 10
  • DOI: 10.1021/om981013c

Reductive heterocoupling mediated by Cp* 2 U(2,2′-bpy)
journal, January 2012

  • Mohammad, Adil; Cladis, Dennis P.; Forrest, William P.
  • Chem. Commun., Vol. 48, Issue 11
  • DOI: 10.1039/C2CC16200H

Catalytic Hydrosilylation of Ketones Using a Co/Zr Heterobimetallic Complex: Evidence for an Unusual Mechanism Involving Ketyl Radicals
journal, February 2013

  • Zhou, Wen; Marquard, Seth L.; Bezpalko, Mark W.
  • Organometallics, Vol. 32, Issue 6
  • DOI: 10.1021/om301194g

Organoactinide phosphine/phosphite coordination chemistry. Facile hydride-induced dealkoxylation and the formation of actinide phosphinidene complexes
journal, May 1984

  • Duttera, Michael R.; Day, Victor W.; Marks, Tobin J.
  • Journal of the American Chemical Society, Vol. 106, Issue 10
  • DOI: 10.1021/ja00322a028

Reactivity of a triamidoamine complex of trivalent uranium
journal, March 2002

  • Roussel, Paul; Boaretto, Rita; Kingsley, Andrew J.
  • Journal of the Chemical Society, Dalton Transactions, Issue 7
  • DOI: 10.1039/b108584k

Oxidation Chemistry of Uranium(III) Complexes of Tpa:  Synthesis and Structural Studies of Oxo, Hydroxo, and Alkoxo Complexes of Uranium(IV)
journal, September 2003

  • Karmazin, Lydia; Mazzanti, Marinella; Pécaut, Jacques
  • Inorganic Chemistry, Vol. 42, Issue 19
  • DOI: 10.1021/ic0343004

Dimeric Rare-Earth BINOLate Complexes: Activation of 1,4-Benzoquinone through Lewis Acid Promoted Potential Shifts
journal, March 2013

  • Robinson, Jerome R.; Booth, Corwin H.; Carroll, Patrick J.
  • Chemistry - A European Journal, Vol. 19, Issue 19
  • DOI: 10.1002/chem.201300026

Use of Alkylsodium Reagents for the Synthesis of Trivalent Uranium Alkyl Complexes
journal, May 2012

  • Matson, Ellen M.; Forrest, William P.; Fanwick, Phillip E.
  • Organometallics, Vol. 31, Issue 12
  • DOI: 10.1021/om3002763

A short history of SHELX
journal, December 2007

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
  • DOI: 10.1107/S0108767307043930

Stereochemistry of dissolving metal reduction of ketones
journal, January 1977


Pinacol versus para coupling of aromatic ketones
journal, September 1997


Dearomatizing Radical Cyclizations and Cyclization Cascades Triggered by Electron-Transfer Reduction of Amide-Type Carbonyls
journal, January 2017

  • Huang, Huan-Ming; Procter, David J.
  • Journal of the American Chemical Society, Vol. 139, Issue 4
  • DOI: 10.1021/jacs.6b12077

Electrochemical models for cytochrome P-450. N-Demethylation of tertiary amides by anodic oxidation
journal, May 1989

  • Hall, Larry R.; Iwamoto, Reynold T.; Hanzlik, Robert P.
  • The Journal of Organic Chemistry, Vol. 54, Issue 10
  • DOI: 10.1021/jo00271a040

Structural and Spectroscopic Characterization of a Charge-Separated Uranium Benzophenone Ketyl Radical Complex
journal, May 2008

  • Lam, Oanh P.; Anthon, Christian; Heinemann, Frank W.
  • Journal of the American Chemical Society, Vol. 130, Issue 20
  • DOI: 10.1021/ja801007q

Uranium pinacolates as intermediates in the reductive coupling of ketones; X-ray crystal structure of a thf solvate of the uranium bisbenzopinacolate U(Ph4C2O2)2(thf)2(thf = tetrahydrofuran)
journal, January 1991

  • Villiers, Claude; Adam, Raymond; Lance, Monique
  • Journal of the Chemical Society, Chemical Communications, Issue 17
  • DOI: 10.1039/c39910001144

Radical–Radical Cyclization Cascades of Barbiturates Triggered by Electron-Transfer Reduction of Amide-Type Carbonyls
journal, June 2016

  • Huang, Huan-Ming; Procter, David J.
  • Journal of the American Chemical Society, Vol. 138, Issue 24
  • DOI: 10.1021/jacs.6b04086

Metal-ammonia reductions of cyclic aliphatic ketones
journal, November 1983


Selective Reduction of Barbituric Acids Using SmI 2 /H 2 O: Synthesis, Reactivity, and Structural Analysis of Tetrahedral Adducts
journal, October 2013

  • Szostak, Michal; Sautier, Brice; Spain, Malcolm
  • Angewandte Chemie, Vol. 125, Issue 48
  • DOI: 10.1002/ange.201306484

Ketyl titanium complexes of (silox)3Ti (silox = tert-Bu3SiO-)
journal, January 1992

  • Covert, Katharine J.; Wolczanski, Peter T.; Hill, Steven A.
  • Inorganic Chemistry, Vol. 31, Issue 1
  • DOI: 10.1021/ic00027a014

Activation of elemental S, Se and Te with uranium(iii): bridging U–E–U (E = S, Se) and diamond-core complexes U–(E)2–U (E = O, S, Se, Te)
journal, January 2011

  • Lam, Oanh P.; Heinemann, Frank W.; Meyer, Karsten
  • Chemical Science, Vol. 2, Issue 8
  • DOI: 10.1039/c1sc00151e

The analogy between CO and C(CN)2. Part 2.1 Structural properties of N,N-dialkylaminobenzamides and the analogously substituted 2-(phenylmethylene)propanedinitriles
journal, January 2002

  • Karlsen, Hege; Kolsaker, Per; Rømming, Christian
  • Journal of the Chemical Society, Perkin Transactions 2, Issue 3
  • DOI: 10.1039/b105532c

Nachweis von radikalanionen bei der elektrolyse einiger carbon- und sulfonsäureamide an der queciksilberkathode
journal, January 1969


Small molecule activation at uranium coordination complexes: control of reactivity via molecular architecture
journal, January 2006

  • Castro-Rodríguez, Ingrid; Meyer, Karsten
  • Chemical Communications, Issue 13
  • DOI: 10.1039/b513755c

The First Structurally Authenticatedσ-Bonded Organosamarium(II) Derivative and Its Reaction with Benzophenone
journal, January 1997

  • Clegg, William; Izod, Keith; O'Shaughnessy, Paul
  • Angewandte Chemie International Edition in English, Vol. 36, Issue 24
  • DOI: 10.1002/anie.199728151

A mechanistic study of the reductive coupling of acetone with uranium compounds
journal, January 1998

  • Ephritikhine, Michel; Maury, Olivier; Villiers, Claude
  • Journal of the Chemical Society, Dalton Transactions, Issue 18
  • DOI: 10.1039/a802672f

Strongly coupled binuclear uranium–oxo complexes from uranyl oxo rearrangement and reductive silylation
journal, February 2012

  • Arnold, Polly L.; Jones, Guy M.; Odoh, Samuel O.
  • Nature Chemistry, Vol. 4, Issue 3
  • DOI: 10.1038/nchem.1270

Spontaneous reduction and C–H borylation of arenes mediated by uranium(III) disproportionation
journal, July 2012

  • Arnold, Polly L.; Mansell, Stephen M.; Maron, Laurent
  • Nature Chemistry, Vol. 4, Issue 8
  • DOI: 10.1038/nchem.1392

U III –CN versus U IV –NC Coordination in Tris(silylamide) Complexes
journal, February 2015


Highly Chemoselective Reduction of Amides (Primary, Secondary, Tertiary) to Alcohols using SmI 2 /Amine/H 2 O under Mild Conditions
journal, January 2014

  • Szostak, Michal; Spain, Malcolm; Eberhart, Andrew J.
  • Journal of the American Chemical Society, Vol. 136, Issue 6
  • DOI: 10.1021/ja412578t

Synthesis of Uranium–Ligand Multiple Bonds by Cleavage of a Trityl Protecting Group
journal, December 2013

  • Smiles, Danil E.; Wu, Guang; Hayton, Trevor W.
  • Journal of the American Chemical Society, Vol. 136, Issue 1
  • DOI: 10.1021/ja411423a

One-Electron Reduction of Aromatic Ketones by Low-Valent Lanthanides. Isolation, Structural Characterization, and Reactivity of Lanthanide Ketyl Complexes
journal, February 1998

  • Hou, Zhaomin; Fujita, Akira; Zhang, Yugen
  • Journal of the American Chemical Society, Vol. 120, Issue 4
  • DOI: 10.1021/ja973184z

Tris[bis(trimethylsilyl)amido](trimethylsilylimido)uranium(V)
journal, September 1988

  • Zalkin, A.; Brennan, J. G.; Andersen, R. A.
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 44, Issue 9
  • DOI: 10.1107/S0108270188005116

Electron spin resonance studies of reduction by solvated electrons in liquid ammonia. Part 5.—Aromatic amides and thioamides
journal, January 1972

  • Elson, I. H.; Kemp, T. J.; Stone, T. J.
  • J. Chem. Soc., Faraday Trans. 2, Vol. 68, Issue 0
  • DOI: 10.1039/F29726801452

EasySpin, a comprehensive software package for spectral simulation and analysis in EPR
journal, January 2006


Organic Compounds of Uranium. IV. Uranium(V) Alkoxides
journal, September 1956

  • Jones, R. G.; Bindschadler, E.; Karmas, G.
  • Journal of the American Chemical Society, Vol. 78, Issue 17
  • DOI: 10.1021/ja01598a028

Crystallographic Evidence of a Base-Free Uranium(IV) Terminal Oxo Species
journal, September 2010

  • Kraft, Steven J.; Walensky, Justin; Fanwick, Phillip E.
  • Inorganic Chemistry, Vol. 49, Issue 17
  • DOI: 10.1021/ic101136j

Low co-ordination numbers in lanthanide and actinide compounds. Part I. The preparation and characterization of tris{bis(trimethylsilyl)-amido}lanthanides
journal, January 1973

  • Bradley, Donald C.; Ghotra, Joginder S.; Hart, F. Alan
  • Journal of the Chemical Society, Dalton Transactions, Issue 10
  • DOI: 10.1039/dt9730001021

Divalent lanthanide derivatives in organic synthesis—II
journal, January 1981


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


Chemical Redox Agents for Organometallic Chemistry
journal, January 1996

  • Connelly, Neil G.; Geiger, William E.
  • Chemical Reviews, Vol. 96, Issue 2
  • DOI: 10.1021/cr940053x

Reversible C–C coupling in phenanthroline complexes of divalent samarium and thulium
journal, January 2015

  • Nocton, Grégory; Ricard, Louis
  • Chemical Communications, Vol. 51, Issue 17
  • DOI: 10.1039/C5CC00289C

Segmented contraction scheme for small-core actinide pseudopotential basis sets
journal, March 2004


Trivalent uranium chemistry: molecular structure of [(Me3Si)2N]3U
journal, March 1998


Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules
journal, March 1972

  • Hehre, W. J.; Ditchfield, R.; Pople, J. A.
  • The Journal of Chemical Physics, Vol. 56, Issue 5, p. 2257-2261
  • DOI: 10.1063/1.1677527

    Works referencing / citing this record:

    Synthese und Struktur des ersten Samarium(II)-Komplexes mit σ-gebundenen Alkylliganden und dessen Reaktion mit Benzophenon
    journal, December 1997


    Selective Reduction of Barbituric Acids Using SmI 2 /H 2 O: Synthesis, Reactivity, and Structural Analysis of Tetrahedral Adducts
    journal, October 2013

    • Szostak, Michal; Sautier, Brice; Spain, Malcolm
    • Angewandte Chemie, Vol. 125, Issue 48
    • DOI: 10.1002/ange.201306484

    The First Structurally Authenticatedσ-Bonded Organosamarium(II) Derivative and Its Reaction with Benzophenone
    journal, January 1997

    • Clegg, William; Izod, Keith; O'Shaughnessy, Paul
    • Angewandte Chemie International Edition in English, Vol. 36, Issue 24
    • DOI: 10.1002/anie.199728151

    Selective Reduction of Barbituric Acids Using SmI 2 /H 2 O: Synthesis, Reactivity, and Structural Analysis of Tetrahedral Adducts
    journal, October 2013

    • Szostak, Michal; Sautier, Brice; Spain, Malcolm
    • Angewandte Chemie International Edition, Vol. 52, Issue 48
    • DOI: 10.1002/anie.201306484

    Dimeric Rare-Earth BINOLate Complexes: Activation of 1,4-Benzoquinone through Lewis Acid Promoted Potential Shifts
    journal, March 2013

    • Robinson, Jerome R.; Booth, Corwin H.; Carroll, Patrick J.
    • Chemistry - A European Journal, Vol. 19, Issue 19
    • DOI: 10.1002/chem.201300026

    Enhancing the Value of Free Metals in the Synthesis of Lanthanoid Formamidinates: Is a Co-oxidant Needed?
    journal, November 2015

    • Deacon, Glen B.; Junk, Peter C.; Werner, Daniel
    • Chemistry - A European Journal, Vol. 22, Issue 1
    • DOI: 10.1002/chem.201502953

    Trivalent Cerium and Praseodymium Aromatic Ketone Adducts
    journal, November 2012

    • Crozier, Alan R.; Törnroos, Karl W.; Maichle-Mössmer, Cäcilia
    • European Journal of Inorganic Chemistry, Vol. 2013, Issue 3
    • DOI: 10.1002/ejic.201201171

    Divalent lanthanide derivatives in organic synthesis—II
    journal, January 1981


    EasySpin, a comprehensive software package for spectral simulation and analysis in EPR
    journal, January 2006


    Bis(pentamethylcyclopentadienyl) U(III) oxide and U(IV) oxide carbene complexes
    journal, November 2004


    Segmented contraction scheme for small-core actinide pseudopotential basis sets
    journal, March 2004


    U III –CN versus U IV –NC Coordination in Tris(silylamide) Complexes
    journal, February 2015


    Spectroscopic and Structural Elucidation of Uranium Dioxophenoxazine Complexes
    journal, June 2015


    Elucidating the Mechanism of Uranium Mediated Diazene N═N Bond Cleavage
    journal, November 2016


    [2π+2π] Cycloaddition of Isocyanates to Uranium(IV) Imido Complexes for the Synthesis of U(IV) κ 2 -Ureato Compounds
    journal, February 2017


    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


    Metal-ammonia reductions of cyclic aliphatic ketones
    journal, November 1983


    Magnetic Susceptibility of Uranium Complexes
    journal, August 2014

    • Kindra, Douglas R.; Evans, William J.
    • Chemical Reviews, Vol. 114, Issue 18
    • DOI: 10.1021/cr500242w

    Chemical Redox Agents for Organometallic Chemistry
    journal, January 1996

    • Connelly, Neil G.; Geiger, William E.
    • Chemical Reviews, Vol. 96, Issue 2
    • DOI: 10.1021/cr940053x

    Diamagnetic Corrections and Pascal's Constants
    journal, April 2008

    • Bain, Gordon A.; Berry, John F.
    • Journal of Chemical Education, Vol. 85, Issue 4
    • DOI: 10.1021/ed085p532

    Ketyl titanium complexes of (silox)3Ti (silox = tert-Bu3SiO-)
    journal, January 1992

    • Covert, Katharine J.; Wolczanski, Peter T.; Hill, Steven A.
    • Inorganic Chemistry, Vol. 31, Issue 1
    • DOI: 10.1021/ic00027a014

    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

    • Avens, Larry R.; Bott, Simon G.; Clark, David L.
    • Inorganic Chemistry, Vol. 33, Issue 10
    • DOI: 10.1021/ic00088a030

    Nuclear magnetic resonance and chemical studies of uranium(V) alkoxides
    journal, October 1983

    • Eller, P. Gary; Vergamini, P. J.
    • Inorganic Chemistry, Vol. 22, Issue 22
    • DOI: 10.1021/ic00164a005

    Oxidation Chemistry of Uranium(III) Complexes of Tpa:  Synthesis and Structural Studies of Oxo, Hydroxo, and Alkoxo Complexes of Uranium(IV)
    journal, September 2003

    • Karmazin, Lydia; Mazzanti, Marinella; Pécaut, Jacques
    • Inorganic Chemistry, Vol. 42, Issue 19
    • DOI: 10.1021/ic0343004

    Synthesis and Characterization of N-Heterocyclic Carbene Complexes of Uranium(III)
    journal, February 2004

    • Nakai, Hidetaka; Hu, Xile; Zakharov, Lev N.
    • Inorganic Chemistry, Vol. 43, Issue 3
    • DOI: 10.1021/ic035142j

    Crystallographic Evidence of a Base-Free Uranium(IV) Terminal Oxo Species
    journal, September 2010

    • Kraft, Steven J.; Walensky, Justin; Fanwick, Phillip E.
    • Inorganic Chemistry, Vol. 49, Issue 17
    • DOI: 10.1021/ic101136j

    Multielectron C–O Bond Activation Mediated by a Family of Reduced Uranium Complexes
    journal, March 2014

    • Kiernicki, John J.; Newell, Brian S.; Matson, Ellen M.
    • Inorganic Chemistry, Vol. 53, Issue 7
    • DOI: 10.1021/ic500012x

    Anomalous One-Electron Processes in the Chemistry of Uranium Nitrogen Multiple Bonds
    journal, August 2014

    • Mullane, Kimberly C.; Lewis, Andrew J.; Yin, Haolin
    • Inorganic Chemistry, Vol. 53, Issue 17
    • DOI: 10.1021/ic501149u

    Tris((hexamethyldisilyl)amido)uranium(III): preparation and coordination chemistry
    journal, June 1979


    Reactivity of Bulky Formamidinatosamarium(II or III) Complexes with C═O and C═S Bonds
    journal, November 2014

    • Deacon, Glen B.; Junk, Peter C.; Wang, Jun
    • Inorganic Chemistry, Vol. 53, Issue 23
    • DOI: 10.1021/ic502181g

    Organoactinide phosphine/phosphite coordination chemistry. Facile hydride-induced dealkoxylation and the formation of actinide phosphinidene complexes
    journal, May 1984

    • Duttera, Michael R.; Day, Victor W.; Marks, Tobin J.
    • Journal of the American Chemical Society, Vol. 106, Issue 10
    • DOI: 10.1021/ja00322a028

    Organic Compounds of Uranium. IV. Uranium(V) Alkoxides
    journal, September 1956

    • Jones, R. G.; Bindschadler, E.; Karmas, G.
    • Journal of the American Chemical Society, Vol. 78, Issue 17
    • DOI: 10.1021/ja01598a028

    Anhydrous Photochemical Uranyl(VI) Reduction:  Unprecedented Retention of Equatorial Coordination Accompanying Reversible Axial Oxo/Alkoxide Exchange
    journal, November 2006

    • Kannan, Shanmugaperumal; Vaughn, Anthony E.; Weis, Eric M.
    • Journal of the American Chemical Society, Vol. 128, Issue 43
    • DOI: 10.1021/ja065822w

    Charge-Separation in Uranium Diazomethane Complexes Leading to C−H Activation and Chemical Transformation
    journal, March 2008

    • Lam, Oanh P.; Feng, Patrick L.; Heinemann, Frank W.
    • Journal of the American Chemical Society, Vol. 130, Issue 9
    • DOI: 10.1021/ja0766472

    Synthesis of a Nitrido-Substituted Analogue of the Uranyl Ion, [N═U═O] +
    journal, May 2010

    • Fortier, Skye; Wu, Guang; Hayton, Trevor W.
    • Journal of the American Chemical Society, Vol. 132, Issue 20
    • DOI: 10.1021/ja101567h

    A Complete Family of Terminal Uranium Chalcogenides, [U(E)(N{SiMe 3 } 2 ) 3 ] (E = O, S, Se, Te)
    journal, September 2012

    • Brown, Jessie L.; Fortier, Skye; Lewis, Richard A.
    • Journal of the American Chemical Society, Vol. 134, Issue 37
    • DOI: 10.1021/ja305712m

    Synthesis of Uranium–Ligand Multiple Bonds by Cleavage of a Trityl Protecting Group
    journal, December 2013

    • Smiles, Danil E.; Wu, Guang; Hayton, Trevor W.
    • Journal of the American Chemical Society, Vol. 136, Issue 1
    • DOI: 10.1021/ja411423a

    Highly Chemoselective Reduction of Amides (Primary, Secondary, Tertiary) to Alcohols using SmI 2 /Amine/H 2 O under Mild Conditions
    journal, January 2014

    • Szostak, Michal; Spain, Malcolm; Eberhart, Andrew J.
    • Journal of the American Chemical Society, Vol. 136, Issue 6
    • DOI: 10.1021/ja412578t

    Reversible Sigma C–C Bond Formation Between Phenanthroline Ligands Activated by (C 5 Me 5 ) 2 Yb
    journal, June 2014

    • Nocton, Grégory; Lukens, Wayne W.; Booth, Corwin H.
    • Journal of the American Chemical Society, Vol. 136, Issue 24
    • DOI: 10.1021/ja502271q

    Structural and Spectroscopic Characterization of a Charge-Separated Uranium Benzophenone Ketyl Radical Complex
    journal, May 2008

    • Lam, Oanh P.; Anthon, Christian; Heinemann, Frank W.
    • Journal of the American Chemical Society, Vol. 130, Issue 20
    • DOI: 10.1021/ja801007q

    Polynuclear Cation−Cation Complexes of Pentavalent Uranyl: Relating Stability and Magnetic Properties to Structure
    journal, December 2008

    • Nocton, Grégory; Horeglad, Pawel; Pécaut, Jacques
    • Journal of the American Chemical Society, Vol. 130, Issue 49
    • DOI: 10.1021/ja804766r

    Studies on the Mechanism, Selectivity, and Synthetic Utility of Lactone Reduction Using SmI 2 and H 2 O
    journal, October 2009

    • Parmar, Dixit; Duffy, Lorna A.; Sadasivam, Dhandapani V.
    • Journal of the American Chemical Society, Vol. 131, Issue 42
    • DOI: 10.1021/ja906396u

    One-Electron Reduction of Aromatic Ketones by Low-Valent Lanthanides. Isolation, Structural Characterization, and Reactivity of Lanthanide Ketyl Complexes
    journal, February 1998

    • Hou, Zhaomin; Fujita, Akira; Zhang, Yugen
    • Journal of the American Chemical Society, Vol. 120, Issue 4
    • DOI: 10.1021/ja973184z

    Radical–Radical Cyclization Cascades of Barbiturates Triggered by Electron-Transfer Reduction of Amide-Type Carbonyls
    journal, June 2016

    • Huang, Huan-Ming; Procter, David J.
    • Journal of the American Chemical Society, Vol. 138, Issue 24
    • DOI: 10.1021/jacs.6b04086

    Dearomatizing Radical Cyclizations and Cyclization Cascades Triggered by Electron-Transfer Reduction of Amide-Type Carbonyls
    journal, January 2017

    • Huang, Huan-Ming; Procter, David J.
    • Journal of the American Chemical Society, Vol. 139, Issue 4
    • DOI: 10.1021/jacs.6b12077

    Electrochemical models for cytochrome P-450. N-Demethylation of tertiary amides by anodic oxidation
    journal, May 1989

    • Hall, Larry R.; Iwamoto, Reynold T.; Hanzlik, Robert P.
    • The Journal of Organic Chemistry, Vol. 54, Issue 10
    • DOI: 10.1021/jo00271a040

    Estimating the Limiting Reducing Power of SmI 2 /H 2 O/Amine and YbI 2 /H 2 O/Amine by Efficient Reduction of Unsaturated Hydrocarbons
    journal, February 2006

    • Dahlén, Anders; Nilsson, Åke; Hilmersson, Göran
    • The Journal of Organic Chemistry, Vol. 71, Issue 4
    • DOI: 10.1021/jo052268k

    Allylsamarium Bromide-Mediated Cascade Cyclization of Homoallylic Esters. Synthesis of 2-(2-Hydroxyalkyl)cyclopropanols and 2-(2-Hydroxyethyl)bicyclo[2.1.1]hexan-1-ols
    journal, December 2014

    • Shen, Mengmeng; Tu, Yawei; Xie, Guanqun
    • The Journal of Organic Chemistry, Vol. 80, Issue 1
    • DOI: 10.1021/jo501797w

    Mechanism of SmI 2 /Amine/H 2 O-Promoted Chemoselective Reductions of Carboxylic Acid Derivatives (Esters, Acids, and Amides) to Alcohols
    journal, October 2014

    • Szostak, Michal; Spain, Malcolm; Eberhart, Andrew J.
    • The Journal of Organic Chemistry, Vol. 79, Issue 24
    • DOI: 10.1021/jo5018525

    A Catalytic System Consisting of Vanadium, Chlorosilane, and Aluminum Metal in the Stereoselective Pinacol Coupling Reaction of Benzaldehyde Derivatives
    journal, October 1999

    • Hirao, Toshikazu; Hatano, Bunpei; Imamoto, Yuka
    • The Journal of Organic Chemistry, Vol. 64, Issue 20
    • DOI: 10.1021/jo990902m

    NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist
    journal, May 2010

    • Fulmer, Gregory R.; Miller, Alexander J. M.; Sherden, Nathaniel H.
    • Organometallics, Vol. 29, Issue 9
    • DOI: 10.1021/om100106e

    Use of Alkylsodium Reagents for the Synthesis of Trivalent Uranium Alkyl Complexes
    journal, May 2012

    • Matson, Ellen M.; Forrest, William P.; Fanwick, Phillip E.
    • Organometallics, Vol. 31, Issue 12
    • DOI: 10.1021/om3002763

    Catalytic Hydrosilylation of Ketones Using a Co/Zr Heterobimetallic Complex: Evidence for an Unusual Mechanism Involving Ketyl Radicals
    journal, February 2013

    • Zhou, Wen; Marquard, Seth L.; Bezpalko, Mark W.
    • Organometallics, Vol. 32, Issue 6
    • DOI: 10.1021/om301194g

    Transfer of Ketyls from Alkali Metals to Transition Metals. Formation and Diverse Reactivities of d-Block Transition-Metal Ketyls
    journal, May 1999

    • Hou, Zhaomin; Fujita, Akira; Koizumi, Take-aki
    • Organometallics, Vol. 18, Issue 10
    • DOI: 10.1021/om981013c

    Strongly coupled binuclear uranium–oxo complexes from uranyl oxo rearrangement and reductive silylation
    journal, February 2012

    • Arnold, Polly L.; Jones, Guy M.; Odoh, Samuel O.
    • Nature Chemistry, Vol. 4, Issue 3
    • DOI: 10.1038/nchem.1270

    Spontaneous reduction and C–H borylation of arenes mediated by uranium(III) disproportionation
    journal, July 2012

    • Arnold, Polly L.; Mansell, Stephen M.; Maron, Laurent
    • Nature Chemistry, Vol. 4, Issue 8
    • DOI: 10.1038/nchem.1392

    Harnessing redox activity for the formation of uranium tris(imido) compounds
    journal, July 2014

    • Anderson, Nickolas H.; Odoh, Samuel O.; Yao, Yiyi
    • Nature Chemistry, Vol. 6, Issue 10
    • DOI: 10.1038/nchem.2009

    A mechanistic study of the reductive coupling of acetone with uranium compounds
    journal, January 1998

    • Ephritikhine, Michel; Maury, Olivier; Villiers, Claude
    • Journal of the Chemical Society, Dalton Transactions, Issue 18
    • DOI: 10.1039/a802672f

    The analogy between CO and C(CN)2. Part 2.1 Structural properties of N,N-dialkylaminobenzamides and the analogously substituted 2-(phenylmethylene)propanedinitriles
    journal, January 2002

    • Karlsen, Hege; Kolsaker, Per; Rømming, Christian
    • Journal of the Chemical Society, Perkin Transactions 2, Issue 3
    • DOI: 10.1039/b105532c

    Reactivity of a triamidoamine complex of trivalent uranium
    journal, March 2002

    • Roussel, Paul; Boaretto, Rita; Kingsley, Andrew J.
    • Journal of the Chemical Society, Dalton Transactions, Issue 7
    • DOI: 10.1039/b108584k

    Small molecule activation at uranium coordination complexes: control of reactivity via molecular architecture
    journal, January 2006

    • Castro-Rodríguez, Ingrid; Meyer, Karsten
    • Chemical Communications, Issue 13
    • DOI: 10.1039/b513755c

    Activation of elemental S, Se and Te with uranium(iii): bridging U–E–U (E = S, Se) and diamond-core complexes U–(E)2–U (E = O, S, Se, Te)
    journal, January 2011

    • Lam, Oanh P.; Heinemann, Frank W.; Meyer, Karsten
    • Chemical Science, Vol. 2, Issue 8
    • DOI: 10.1039/c1sc00151e

    Uranium pinacolates as intermediates in the reductive coupling of ketones; X-ray crystal structure of a thf solvate of the uranium bisbenzopinacolate U(Ph4C2O2)2(thf)2(thf = tetrahydrofuran)
    journal, January 1991

    • Villiers, Claude; Adam, Raymond; Lance, Monique
    • Journal of the Chemical Society, Chemical Communications, Issue 17
    • DOI: 10.1039/c39910001144

    Low co-ordination numbers in lanthanide and actinide compounds. Part I. The preparation and characterization of tris{bis(trimethylsilyl)-amido}lanthanides
    journal, January 1973

    • Bradley, Donald C.; Ghotra, Joginder S.; Hart, F. Alan
    • Journal of the Chemical Society, Dalton Transactions, Issue 10
    • DOI: 10.1039/dt9730001021

    Redox reactions of dopamine transients in aqueous solution: a pulse radiolysis study
    journal, January 1994

    • Maity, Dilip K.; Mohan, Hari; Mittal, Jai P.
    • Journal of the Chemical Society, Perkin Transactions 2, Issue 4
    • DOI: 10.1039/p29940000919

    Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules
    journal, March 1972

    • Hehre, W. J.; Ditchfield, R.; Pople, J. A.
    • The Journal of Chemical Physics, Vol. 56, Issue 5, p. 2257-2261
    • DOI: 10.1063/1.1677527

    Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide
    journal, May 1994

    • Küchle, W.; Dolg, M.; Stoll, H.
    • The Journal of Chemical Physics, Vol. 100, Issue 10
    • DOI: 10.1063/1.466847

    A short history of SHELX
    journal, December 2007

    • Sheldrick, George M.
    • Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
    • DOI: 10.1107/s0108767307043930

    A Linear, O-Coordinated  1-CO2 Bound to Uranium
    journal, September 2004


    Stereochemistry of dissolving metal reduction of ketones
    journal, January 1977


    Ultrafast amidation of esters using lithium amides under aerobic ambient temperature conditions in sustainable solvents
    journal, January 2020

    • Fairley, Michael; Bole, Leonie J.; Mulks, Florian F.
    • Chemical Science
    • DOI: 10.1039/d0sc01349h