skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: CO2 conversion to phenyl isocyanates by uranium(vi) bis(imido) complexes

Abstract

U( vi ) trans -bis(imido) complexes [U(κ 4 {( tBu2 ArO) 2 Me 2 -cyclam})(NPh)(NPh R )] react with CO 2 to afford U( vi ) trans -[OUNR] 2+ complexes with elimination of isocyanates. These are unprecedented examples of CO 2 cleavage mediated by U( vi ) imido complexes.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]
  1. Univ. of Lisbon (Portugal)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1631623
Alternate Identifier(s):
OSTI ID: 1578137
Grant/Contract Number:  
AC02-05CH11231; AC02-05CH1123
Resource Type:
Accepted Manuscript
Journal Name:
ChemComm
Additional Journal Information:
Journal Volume: 56; Journal Issue: 3; Journal ID: ISSN 1359-7345
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Maria, Leonor, Bandeira, Nuno A. G., Marçalo, Joaquim, Santos, Isabel C., and Gibson, John K. CO2 conversion to phenyl isocyanates by uranium(vi) bis(imido) complexes. United States: N. p., 2019. Web. https://doi.org/10.1039/c9cc07411b.
Maria, Leonor, Bandeira, Nuno A. G., Marçalo, Joaquim, Santos, Isabel C., & Gibson, John K. CO2 conversion to phenyl isocyanates by uranium(vi) bis(imido) complexes. United States. https://doi.org/10.1039/c9cc07411b
Maria, Leonor, Bandeira, Nuno A. G., Marçalo, Joaquim, Santos, Isabel C., and Gibson, John K. Thu . "CO2 conversion to phenyl isocyanates by uranium(vi) bis(imido) complexes". United States. https://doi.org/10.1039/c9cc07411b. https://www.osti.gov/servlets/purl/1631623.
@article{osti_1631623,
title = {CO2 conversion to phenyl isocyanates by uranium(vi) bis(imido) complexes},
author = {Maria, Leonor and Bandeira, Nuno A. G. and Marçalo, Joaquim and Santos, Isabel C. and Gibson, John K.},
abstractNote = {U( vi ) trans -bis(imido) complexes [U(κ 4 {( tBu2 ArO) 2 Me 2 -cyclam})(NPh)(NPh R )] react with CO 2 to afford U( vi ) trans -[OUNR] 2+ complexes with elimination of isocyanates. These are unprecedented examples of CO 2 cleavage mediated by U( vi ) imido complexes.},
doi = {10.1039/c9cc07411b},
journal = {ChemComm},
number = 3,
volume = 56,
place = {United States},
year = {2019},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Carbon oxygenate transformations by actinide compounds and catalysts
journal, January 2017


Metal–ligand multiple bonding in uranium: structure and reactivity
journal, January 2010


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

A Series of Uranium (IV, V, VI) Tritylimido Complexes, Their Molecular and Electronic Structures and Reactivity with CO 2
journal, November 2014

  • Schmidt, Anna-Corina; Heinemann, Frank W.; Maron, Laurent
  • Inorganic Chemistry, Vol. 53, Issue 24
  • DOI: 10.1021/ic5023517

The insertion of carbon dioxide into actinide alkyl and hydride bonds
journal, September 1985


Insertion Reactivity of CO 2 , PhNCO, Me 3 CC≡N, and Me 3 CN≡C with the Uranium−Alkynyl Bonds in (C 5 Me 5 ) 2 U(C≡CPh) 2
journal, February 2010

  • Evans, William J.; Walensky, Justin R.; Ziller, Joseph W.
  • Organometallics, Vol. 29, Issue 4
  • DOI: 10.1021/om901006t

Small-Molecule Activation at Uranium(III)
journal, April 2013

  • Gardner, Benedict M.; Liddle, Stephen T.
  • European Journal of Inorganic Chemistry, Vol. 2013, Issue 22-23
  • DOI: 10.1002/ejic.201300111

Synthesis of Imido Analogs of the Uranyl Ion
journal, December 2005


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

Exchange of an Imido Ligand in Bis(imido) Complexes of Uranium
journal, October 2006

  • Hayton, Trevor W.; Boncella, James M.; Scott, Brian L.
  • Journal of the American Chemical Society, Vol. 128, Issue 39
  • DOI: 10.1021/ja064400j

Pendant Arm Functionalized Benzamidinate Titanium Imido Compounds:  Experimental and Computational Studies of Their Reactions with CO 2
journal, May 2005

  • Boyd, Catherine L.; Clot, Eric; Guiducci, Aldo E.
  • Organometallics, Vol. 24, Issue 10
  • DOI: 10.1021/om049026f

Imido Exchange in Bis(imido) Uranium(VI) Complexes with Aryl Isocyanates
journal, March 2008

  • Spencer, Liam P.; Yang, Ping; Scott, Brian L.
  • Journal of the American Chemical Society, Vol. 130, Issue 10
  • DOI: 10.1021/ja7107454

Preparation and Reactivity of the Versatile Uranium(IV) Imido Complexes U(NAr)Cl 2 (R 2 bpy) 2 (R = Me, t Bu) and U(NAr)Cl 2 (tppo) 3
journal, August 2014

  • Jilek, Robert E.; Tomson, Neil C.; Shook, Ryan L.
  • Inorganic Chemistry, Vol. 53, Issue 18
  • DOI: 10.1021/ic5014208

Managing the Computational Chemistry Big Data Problem: The ioChem-BD Platform
journal, December 2014

  • Álvarez-Moreno, M.; de Graaf, C.; López, N.
  • Journal of Chemical Information and Modeling, Vol. 55, Issue 1
  • DOI: 10.1021/ci500593j

Synthesis of ureas from titanium imido complexes using CO 2 as a C-1 reagent at ambient temperature and pressure
journal, January 2012

  • Anderson, James C.; Moreno, Rafael Bou
  • Org. Biomol. Chem., Vol. 10, Issue 7
  • DOI: 10.1039/C1OB06576A

Carbon Dioxide Activation with Sterically Pressured Mid- and High-Valent Uranium Complexes
journal, September 2008

  • Bart, Suzanne C.; Anthon, Christian; Heinemann, Frank W.
  • Journal of the American Chemical Society, Vol. 130, Issue 37
  • DOI: 10.1021/ja804263w

Terminal Uranium(V/VI) Nitride Activation of Carbon Dioxide and Carbon Disulfide: Factors Governing Diverse and Well-Defined Cleavage and Redox Reactions
journal, January 2017

  • Cleaves, Peter A.; Kefalidis, Christos E.; Gardner, Benedict M.
  • Chemistry - A European Journal, Vol. 23, Issue 12
  • DOI: 10.1002/chem.201605620

Chemistry with ADF
journal, January 2001

  • te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.
  • Journal of Computational Chemistry, Vol. 22, Issue 9, p. 931-967
  • DOI: 10.1002/jcc.1056

Aryl Isocyanate, Carbodiimide, and Isocyanide Prepared from Carbon Dioxide. A Metathetical Group-Transfer Tale Involving a Titanium−Imide Zwitterion
journal, January 2006

  • Kilgore, Uriah J.; Basuli, Falguni; Huffman, John C.
  • Inorganic Chemistry, Vol. 45, Issue 2
  • DOI: 10.1021/ic052065e

Recent developments in actinide–ligand multiple bonding
journal, January 2013


Carbon Dioxide Reduction and Carbon Monoxide Activation Employing a Reactive Uranium(III) Complex
journal, August 2005

  • Castro-Rodriguez, Ingrid; Meyer, Karsten
  • Journal of the American Chemical Society, Vol. 127, Issue 32
  • DOI: 10.1021/ja053497r

Reductive disproportionation of carbon dioxide to carbonate and squarate products using a mixed-sandwich U( iii ) complex
journal, January 2008

  • Summerscales, Owen T.; Frey, Alistair S. P.; Cloke, F. Geoffrey N.
  • Chem. Commun., Issue 2
  • DOI: 10.1039/B815576C

Uranium-mediated reductive conversion of CO2 to CO and carbonate in a single-vessel, closed synthetic cycle
journal, January 2012

  • Schmidt, Anna-Corina; Nizovtsev, Alexey V.; Scheurer, Andreas
  • Chemical Communications, Vol. 48, Issue 69
  • DOI: 10.1039/c2cc34150f

CO 2 conversion to isocyanate via multiple N–Si bond cleavage at a bulky uranium( iii ) complex
journal, January 2015

  • Camp, Clément; Chatelain, Lucile; Kefalidis, Christos E.
  • Chemical Communications, Vol. 51, Issue 84
  • DOI: 10.1039/C5CC06707C

Reactions of cyclopentadienyl-amidinate titanium imido compounds with CO2: cycloaddition-extrusion vs. cycloaddition-insertion
journal, January 2009

  • Guiducci, Aldo E.; Boyd, Catherine L.; Clot, Eric
  • Dalton Transactions, Issue 30
  • DOI: 10.1039/b901774g

From Amides to Amidines:  Preparations of Imidoylbenzotriazoles and Arylaminoheterocycles
journal, February 2001

  • Katritzky, Alan R.; Huang, Tian-Bao; Voronkov, Michael V.
  • The Journal of Organic Chemistry, Vol. 66, Issue 3
  • DOI: 10.1021/jo0013397

Comment on “Generalized Gradient Approximation Made Simple”
journal, January 1998


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


Electronic Structure and Bonding in Actinyl Ions and their Analogs
journal, May 2007

  • Denning, Robert G.
  • The Journal of Physical Chemistry A, Vol. 111, Issue 20
  • DOI: 10.1021/jp071061n

Synthesis, Characterization, and Reactivity of a Uranium(VI) Carbene Imido Oxo Complex
journal, May 2014

  • Lu, Erli; Cooper, Oliver J.; McMaster, Jonathan
  • Angewandte Chemie International Edition, Vol. 53, Issue 26
  • DOI: 10.1002/anie.201403892

Controlling selectivity in the reductive activation of CO 2 by mixed sandwich uranium( iii ) complexes
journal, January 2014

  • Tsoureas, Nikolaos; Castro, Ludovic; Kilpatrick, Alexander F. R.
  • Chem. Sci., Vol. 5, Issue 10
  • DOI: 10.1039/C4SC01401D

Multimetallic Cooperativity in Uranium-Mediated CO 2 Activation
journal, April 2014

  • Cooper, Oliver; Camp, Clément; Pécaut, Jacques
  • Journal of the American Chemical Society, Vol. 136, Issue 18
  • DOI: 10.1021/ja5017624

Bispentamethylcyclopentadienyl uranium(IV) thiolate compounds. Synthesis and reactions with CO2 and CS2
journal, May 1999

  • Lescop, Christophe; Arliguie, Thérèse; Lance, Monique
  • Journal of Organometallic Chemistry, Vol. 580, Issue 1
  • DOI: 10.1016/S0022-328X(98)01139-5

Benchmarking Density Functional Methods against the S66 and S66x8 Datasets for Non-Covalent Interactions
journal, November 2011


    Works referencing / citing this record:

    Divergent uranium- versus phosphorus-based reduction of Me 3 SiN 3 with steric modification of phosphido ligands
    journal, January 2020

    • Ward, Robert J.; Rungthanaphatsophon, Pokpong; Rosal, Iker del
    • Chemical Science, Vol. 11, Issue 22
    • DOI: 10.1039/d0sc02261f