Isolation of a TMTAA-Based Radical in Uranium bis-TMTAA Complexes

Hohloch, Stephan; Garner, Mary E.; Booth, Corwin H.; Lukens, Wayne W.; Gould, Colin A.; Lussier, Daniel J.; Maron, Laurent; Arnold, John

doi:10.1002/ange.201810971

Title: Isolation of a TMTAA-Based Radical in Uranium bis-TMTAA Complexes

Journal Article · 16 October 2018 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.201810971 · OSTI ID:1798733

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Univ. of California, Berkeley, CA (United States); Univ. of Paderborn (Germany)
Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of Toulouse (France)

Here, we report the synthesis, characterization, and electronic structure studies of a series of thorium(IV) and uranium(IV) bis-tetramethyltetraazaannulene complexes. These sandwich complexes show remarkable stability towards air and moisture, even at elevated temperatures. Electrochemical studies show the uranium complex to be stable in three different oxidation states; isolation of the oxidized species reveals a rare case of a non-innocent tetramethyltetraazaannulene (TMTAA) ligand.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: German Academic Exchange Service (DAAD); National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1798733

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 49 Vol. 130; ISSN 0044-8249

Publisher:: German Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (56)

Hexakisamidokomplexe des Urans Meyer, Karsten; Mindiola, Daniel J.; Baker, Thomas A. Angewandte Chemie, Vol. 112, Issue 17 https://doi.org/10.1002/1521-3757(20000901)112:17<3191::AID-ANGE3191>3.0.CO;2-0	journal	September 2000
Uranium Hexakisamido Complexes Meyer, Karsten; Mindiola, Daniel J.; Baker, Thomas A. Angewandte Chemie, Vol. 39, Issue 17 https://doi.org/10.1002/1521-3773(20000901)39:17<3063::AID-ANIE3063>3.0.CO;2-0	journal	September 2000
Hidden Noninnocence: Theoretical and Experimental Evidence for Redox Activity of a β-Diketiminate(1−) Ligand Khusniyarov , Marat M.; Bill, Eckhard; Weyhermüller, Thomas Angewandte Chemie, Vol. 123, Issue 7 https://doi.org/10.1002/ange.201005953	journal	January 2011
The Inherent Single-Molecule Magnet Character of Trivalent Uranium Moro, Fabrizio; Mills, David P.; Liddle, Stephen T. Angewandte Chemie, Vol. 125, Issue 12 https://doi.org/10.1002/ange.201208015	journal	February 2013
Die Renaissance der nichtwässrigen Uranchemie Liddle, Stephen T. Angewandte Chemie, Vol. 127, Issue 30 https://doi.org/10.1002/ange.201412168	journal	June 2015
Carbon-Nitrogen Bond Cleavage by a Thorium-NHC-bpy Complex Garner, Mary E.; Hohloch, Stephan; Maron, Laurent Angewandte Chemie, Vol. 128, Issue 44 https://doi.org/10.1002/ange.201607899	journal	September 2016
Hidden Noninnocence: Theoretical and Experimental Evidence for Redox Activity of a β-Diketiminate(1−) Ligand Khusniyarov , Marat M.; Bill, Eckhard; Weyhermüller, Thomas Angewandte Chemie International Edition, Vol. 50, Issue 7 https://doi.org/10.1002/anie.201005953	journal	January 2011
The Inherent Single-Molecule Magnet Character of Trivalent Uranium Moro, Fabrizio; Mills, David P.; Liddle, Stephen T. Angewandte Chemie International Edition, Vol. 52, Issue 12 https://doi.org/10.1002/anie.201208015	journal	February 2013
The Renaissance of Non-Aqueous Uranium Chemistry Liddle, Stephen T. Angewandte Chemie International Edition, Vol. 54, Issue 30 https://doi.org/10.1002/anie.201412168	journal	June 2015
Carbon-Nitrogen Bond Cleavage by a Thorium-NHC-bpy Complex Garner, Mary E.; Hohloch, Stephan; Maron, Laurent Angewandte Chemie International Edition, Vol. 55, Issue 44 https://doi.org/10.1002/anie.201607899	journal	October 2016
Aminomethylen-?-dicarbonylverbindungen als Komplexliganden. V. Neue konjugiert-unges�ttigte Neutralkomplexe mit vierzehngliedrigen, makrozyklischen Liganden J�ger, E. -G. Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 364, Issue 3-4 https://doi.org/10.1002/zaac.19693640308	journal	January 1969
Is there a molecular analogue of a Kondo singlet state? Neumann, C. S.; Fulde, P. Zeitschrift f�r Physik B Condensed Matter, Vol. 74, Issue 3 https://doi.org/10.1007/BF01307872	journal	September 1989
π-cyclopentadienyl compounds of uranium-IV and thorium-IV Reynolds, L. T.; Wilkinson, G. Journal of Inorganic and Nuclear Chemistry, Vol. 2, Issue 4 https://doi.org/10.1016/0022-1902(56)80051-1	journal	April 1956
Formally tetravalent cerium and thorium compounds: a configuration interaction study of cerocene Ce(C8H8)2 and thorocene Th(C8H8)2 using energy-adjusted quasirelativistic ab initio pseudopotentials Dolg, M.; Fulde, P.; Stoll, H. Chemical Physics, Vol. 195, Issue 1-3 https://doi.org/10.1016/0301-0104(94)00363-F	journal	June 1995
Unusual metalloporphyrins : thorium and uranium complexes of octaethylporphyrin. Dormond, Alain; Belkalem, Boussad; Guilard, Roger Polyhedron, Vol. 3, Issue 1 https://doi.org/10.1016/S0277-5387(00)84721-X	journal	January 1984
Dibenzo[b,i][1,4,8,11]tetra-azacyclotetradecine complexes—I. W(CO)4(tmtaa) Cotton, F. Albert; Czuchajowska, Joanna Polyhedron, Vol. 9, Issue 9 https://doi.org/10.1016/S0277-5387(00)86898-9	journal	January 1990
Organoactinides in catalysis Barnea, E.; Eisen, M. Coordination Chemistry Reviews, Vol. 250, Issue 7-8 https://doi.org/10.1016/j.ccr.2005.12.007	journal	April 2006
Synthesis, characterization, and epoxide ring-opening reactivity of thorium-NHC-bpy complexes Garner, Mary E.; Lohrey, Trevor D.; Hohloch, Stephan Journal of Organometallic Chemistry, Vol. 857 https://doi.org/10.1016/j.jorganchem.2017.09.006	journal	February 2018
Uranyl Coordination by the 14-Membered Macrocycle Dibenzotetramethyltetraaza[14]annulene Pedrick, Elizabeth A.; Assefa, Mikiyas K.; Wakefield, Megan E. Inorganic Chemistry, Vol. 56, Issue 11 https://doi.org/10.1021/acs.inorgchem.7b00700	journal	May 2017
Cerium Tetrakis(tropolonate) and Cerium Tetrakis(acetylacetonate) Are Not Diamagnetic but Temperature-Independent Paramagnets Halbach, Robert L.; Nocton, Grégory; Booth, Corwin H. Inorganic Chemistry, Vol. 57, Issue 12 https://doi.org/10.1021/acs.inorgchem.8b00928	journal	June 2018
Oxidation of the 14-Membered Macrocycle Dibenzotetramethyltetraaza[14]annulene upon Ligation to the Uranyl Ion Assefa, Mikiyas K.; Pedrick, Elizabeth A.; Wakefield, Megan E. Inorganic Chemistry, Vol. 57, Issue 14 https://doi.org/10.1021/acs.inorgchem.8b00966	journal	June 2018
A New Supporting Ligand in Actinide Chemistry Leads to Reactive Bis(NHC)borate-Supported Thorium Complexes Garner, Mary E.; Hohloch, Stephan; Maron, Laurent Organometallics, Vol. 35, Issue 17 https://doi.org/10.1021/acs.organomet.6b00467	journal	August 2016
Reductive Elimination of Diphosphine from a Thorium–NHC–Bis(phosphido) Complex Garner, Mary E.; Arnold, John Organometallics, Vol. 36, Issue 23 https://doi.org/10.1021/acs.organomet.7b00301	journal	May 2017
Magnetic Susceptibility of Uranium Complexes Kindra, Douglas R.; Evans, William J. Chemical Reviews, Vol. 114, Issue 18 https://doi.org/10.1021/cr500242w	journal	August 2014
Mono- and bis(dibenzotetramethyltetraaza[14]annulene) complexes of Group IV metals including the structure of the lithium derivative of the macrocyclic ligand De Angelis, Stefania; Solari, Euro; Gallo, Emma Inorganic Chemistry, Vol. 31, Issue 12 https://doi.org/10.1021/ic00038a039	journal	June 1992
Synthesis and characterization of actinide mono and bis porphyrin complexes Girolami, Gregory S.; Milam, Stanley N.; Suslick, Kenneth S. Inorganic Chemistry, Vol. 26, Issue 3 https://doi.org/10.1021/ic00250a001	journal	February 1987
First example of 1:1 actinide-phthalocyanine complexes: synthesis, electrochemical, and spectral characterization of bis(diketonato)thorium(IV) and -uranium(IV) phthalocyaninates Guilard, R.; Dormond, A.; Belkalem, M. Inorganic Chemistry, Vol. 26, Issue 9 https://doi.org/10.1021/ic00256a016	journal	May 1987
Comparison of the Redox Chemistry of Primary and Secondary Amides of U(IV): Isolation of a U(VI) Bis(imido) Complex or a Homoleptic U(VI) Amido Complex Seaman, Lani A.; Fortier, Skye; Wu, Guang Inorganic Chemistry, Vol. 50, Issue 2 https://doi.org/10.1021/ic101847b	journal	January 2011
Single Crystal to Single Crystal Transformation and Hydrogen-Atom Transfer upon Oxidation of a Cerium Coordination Compound Williams, Ursula J.; Mahoney, Brian D.; Lewis, Andrew J. Inorganic Chemistry, Vol. 52, Issue 8 https://doi.org/10.1021/ic4001973	journal	March 2013
Double-decker actinide porphyrins and phthalocyanines. Synthesis and spectroscopic characterization of neutral, oxidized, and reduced homo- and heteroleptic complexes Kadish, K. M.; Moninot, G.; Hu, Y. Journal of the American Chemical Society, Vol. 115, Issue 18 https://doi.org/10.1021/ja00071a028	journal	September 1993
Observation of a new low-energy fluorescent 1(.pi.,.pi.*) excited state in strongly coupled porphyrin dimers Bilsel, Osman; Rodriguez, Juan; Holten, Dewey Journal of the American Chemical Society, Vol. 112, Issue 10 https://doi.org/10.1021/ja00166a075	journal	May 1990
Macrocyclic effect on the stability of copper(II) tetramine complexes Cabbiness, Dale K.; Margerum, Dale W. Journal of the American Chemical Society, Vol. 91, Issue 23 https://doi.org/10.1021/ja01051a091	journal	November 1969
Synthesis and Characterization of Thorium(IV) and Uranium(IV) Corrole Complexes Ward, Ashleigh L.; Buckley, Heather L.; Lukens, Wayne W. Journal of the American Chemical Society, Vol. 135, Issue 37 https://doi.org/10.1021/ja407203s	journal	September 2013
A Homoleptic Uranium(III) Tris(aryl) Complex Boreen, Michael A.; Parker, Bernard F.; Lohrey, Trevor D. Journal of the American Chemical Society, Vol. 138, Issue 49 https://doi.org/10.1021/jacs.6b11182	journal	December 2016
A Thorium Chalcogenolate Series Generated by Atom Insertion into Thorium–Carbon Bonds Settineri, Nicholas S.; Garner, Mary E.; Arnold, John Journal of the American Chemical Society, Vol. 139, Issue 17 https://doi.org/10.1021/jacs.7b02356	journal	April 2017
Thorium Metallacycle Facilitates Catalytic Alkyne Hydrophosphination Garner, Mary E.; Parker, Bernard F.; Hohloch, Stephan Journal of the American Chemical Society, Vol. 139, Issue 37 https://doi.org/10.1021/jacs.7b08323	journal	September 2017
Is Cerocene Really a Ce(III) Compound? All-Electron Spin−Orbit Coupled CASPT2 Calculations on M(η ⁸ -C ₈ H ₈ ) ₂ (M = Th, Pa, Ce) Kerridge, Andrew; Coates, Rosemary; Kaltsoyannis, Nikolas The Journal of Physical Chemistry A, Vol. 113, Issue 12 https://doi.org/10.1021/jp807804w	journal	March 2009
Recent Advances in Organoactinide Chemistry As Exemplified by Cyclopentadienyl Compounds Ephritikhine, Michel Organometallics, Vol. 32, Issue 9 https://doi.org/10.1021/om400145p	journal	March 2013
Cerocene Revisited: The Electronic Structure of and Interconversion Between Ce ₂ (C ₈ H ₈ ) ₃ and Ce(C ₈ H ₈ ) ₂ Walter, Marc D.; Booth, Corwin H.; Lukens, Wayne W. Organometallics, Vol. 28, Issue 3 https://doi.org/10.1021/om7012327	journal	February 2009
Towards uranium catalysts Fox, Alexander R.; Bart, Suzanne C.; Meyer, Karsten Nature, Vol. 455, Issue 7211 https://doi.org/10.1038/nature07372	journal	September 2008
Deoxovanadium( IV ) complexes of the dibenzotetramethyltetra-aza[14]-annulene ligand: formation of products containing thioxo-, µ-nitrido-, and oxidatively coupled ligands Goedken, Virgil L.; Ladd, Judith A. J. Chem. Soc., Chem. Commun., Issue 17 https://doi.org/10.1039/C39810000910	journal	January 1981
Uranium triamidoamine chemistry Gardner, Benedict M.; Liddle, Stephen T. Chemical Communications, Vol. 51, Issue 53 https://doi.org/10.1039/C5CC01360G	journal	January 2015
Improving f-element single molecule magnets Liddle, Stephen T.; van Slageren, Joris Chemical Society Reviews, Vol. 44, Issue 19 https://doi.org/10.1039/C5CS00222B	journal	January 2015
Uranium and thorium complexes of the phosphaethynolate ion Camp, Clément; Settineri, Nicholas; Lefèvre, Julia Chemical Science, Vol. 6, Issue 11 https://doi.org/10.1039/C5SC02150B	journal	January 2015
On the non-innocence of “Nacnacs”: ligand-based reactivity in β-diketiminate supported coordination compounds Camp, Clément; Arnold, John Dalton Transactions, Vol. 45, Issue 37 https://doi.org/10.1039/C6DT02013E	journal	January 2016
New supporting ligands in actinide chemistry: tetramethyltetraazaannulene complexes with thorium and uranium Hohloch, Stephan; Garner, Mary E.; Parker, Bernard F. Dalton Trans., Vol. 46, Issue 40 https://doi.org/10.1039/C7DT02682J	journal	January 2017
Benzoquinonoid-bridged dinuclear actinide complexes Hohloch, Stephan; Pankhurst, James R.; Jaekel, Esther E. Dalton Transactions, Vol. 46, Issue 35 https://doi.org/10.1039/C7DT02728A	journal	January 2017
Dibenzotetraaza[14]annulenes: versatile ligands for transition and main group metal chemistry Mountford, Philip Chemical Society Reviews, Vol. 27, Issue 2 https://doi.org/10.1039/a827105z	journal	January 1998
Synthesis and magnetic properties of cerium macrocyclic complexes with tetramethyldibenzotetraaza[14]annulene, tmtaaH2 Walter, Marc D.; Fandos, Rosa; Andersen, Richard A. New Journal of Chemistry, Vol. 30, Issue 7 https://doi.org/10.1039/b602644c	journal	January 2006
A comparison of the effects of symmetry and magnetoanisotropy on paramagnetic relaxation in related dysprosium single ion magnets Williams, Ursula J.; Mahoney, Brian D.; DeGregorio, Patrick T. Chemical Communications, Vol. 48, Issue 45 https://doi.org/10.1039/c2cc31227a	journal	January 2012
Monocarbon monoxide complexes of iron(II): synthesis and X-ray structural characterization Goedken, Virgil L.; Molin-Case, JoAnn; Whang, Young-ae Journal of the Chemical Society, Chemical Communications, Issue 10 https://doi.org/10.1039/c39730000337	journal	January 1973
Recent developments in actinide–ligand multiple bonding Hayton, Trevor W. Chemical Communications, Vol. 49, Issue 29 https://doi.org/10.1039/c3cc39053e	journal	January 2013
Ground state calculations of di‐π‐cyclooctatetraene cerium Dolg, Michael; Fulde, Peter; Küchle, Wolfgang The Journal of Chemical Physics, Vol. 94, Issue 4 https://doi.org/10.1063/1.459824	journal	February 1991
Self-Contained Kondo Effect in Single Molecules Booth, C. H.; Walter, M. D.; Daniel, M. Physical Review Letters, Vol. 95, Issue 26 https://doi.org/10.1103/PhysRevLett.95.267202	journal	December 2005
A Linear, O-Coordinated 1-CO2 Bound to Uranium Castro-Rodriguez, I. Science, Vol. 305, Issue 5691 https://doi.org/10.1126/science.1102602	journal	September 2004
Molecular Octa-Uranium Rings with Alternating Nitride and Azide Bridges Evans, W. J. Science, Vol. 309, Issue 5742 https://doi.org/10.1126/science.1116452	journal	September 2005

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Structure and magnetism of a tetrahedral uranium( iii ) β-diketiminate complex Boreen, Michael A.; Gould, Colin A.; Booth, Corwin H. Dalton Transactions, Vol. 49, Issue 23 https://doi.org/10.1039/d0dt01599g	journal	January 2020

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Makrocyclen
Nichtunschuldige Liganden
TMTAA
Thorium
Uran

CCDC 1412405: Experimental Crystal Structure Determination Hohloch, Stephan; Garner, Mary E.; Booth, Corwin H. https://doi.org/10.5517/ccdc.csd.cc1jdqg3 The current record is supplemented by this dataset	dataset	January 2019
CCDC 1414028: Experimental Crystal Structure Determination Hohloch, Stephan; Garner, Mary E.; Booth, Corwin H. https://doi.org/10.5517/ccdc.csd.cc1jgdt6 The current record is supplemented by this dataset	dataset	January 2019
CCDC 1488209: Experimental Crystal Structure Determination Hohloch, Stephan; Garner, Mary E.; Booth, Corwin H. https://doi.org/10.5517/ccdc.csd.cc1lylrw The current record is supplemented by this dataset	dataset	January 2019
CCDC 1516432: Experimental Crystal Structure Determination Hohloch, Stephan; Garner, Mary E.; Booth, Corwin H. https://doi.org/10.5517/ccdc.csd.cc1mwz5n The current record is supplemented by this dataset	dataset	January 2019
CCDC 1520550: Experimental Crystal Structure Determination Hohloch, Stephan; Garner, Mary E.; Booth, Corwin H. https://doi.org/10.5517/ccdc.csd.cc1n180z The current record is supplemented by this dataset	dataset	January 2019