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Title: Benzoquinonoid-bridged dinuclear actinide complexes

Abstract

We report here the coordination chemistry of the tripodal tris[2-amido(2-pyridyl)ethyl]amine ligand, L, with thorium(IV) and uranium(IV). Using a salt-metathesis strategy from the potassium salt of this ligand, K 3L, new actinide complexes were isolated, namely the dimeric thorium complex [ThCl(L)] 2 (1) and the monomeric uranium complex UI(THF)(L) (2); under different crystallisation conditions, the dimeric uranium complex is also isolated, [UI(L)] 2 (2-dimer). With the aim of studying electronic phenomena such as magnetic exchange between two actinide ions, we have synthesised the first examples of dinuclear, quinoid-bridged actinide complexes from dianionic 2,5-bis[2,6-(diisopropyl)anilide]-1,4-benzoquinone (Q Dipp) and 2,5-bis[2-(methoxy)anilide]-1,4-benzoquinone (Q OMe) ligands. The resulting complexes are [Th(L)] 2Q Dipp (3), [Th(THF)(L)] 2Q OMe (5) and [U(L)] 2Q OMe (6). The targeted [U(L)] 2Q Dipp complex (4) could not be isolated. All isolated complexes have been characterised by spectroscopic methods and X-ray crystallography. The uranium(IV) complexes 2-dimer and 6 have been studied by SQUID magnetometry but indicate that there is negligible magnetic exchange between the two uranium(IV) ions. The reduced form of 6, [K(18-c-6)][6 -] is unstable and highly sensitive, but X-ray crystallography indicates that it is a novel U IVU IV complex bridged by a quinoid-radical.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [4];  [4]; ORCiD logo [4];  [5]; ORCiD logo [6]; ORCiD logo [4]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Paderborn Univ. (Germany). Dept. of Chemistry
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of Edinburgh, Scotland (United Kingdom). EaStCHEM School of Chemistry
  3. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
  4. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  6. Univ. of Edinburgh, Scotland (United Kingdom). EaStCHEM School of Chemistry
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Paderborn Univ. (Germany)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); National Inst. of Health (NIH) (United States); German Academic Exchange Service (DAAD); German Federal Ministry of Education and Research (BMBF)
OSTI Identifier:
1493246
Grant/Contract Number:  
AC02-05CH11231; CHE-0840505; S10-RR027172
Resource Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 46; Journal Issue: 35; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Hohloch, Stephan, Pankhurst, James R., Jaekel, Esther E., Parker, Bernard F., Lussier, Daniel J., Garner, Mary E., Booth, Corwin H., Love, Jason B., and Arnold, John. Benzoquinonoid-bridged dinuclear actinide complexes. United States: N. p., 2017. Web. doi:10.1039/c7dt02728a.
Hohloch, Stephan, Pankhurst, James R., Jaekel, Esther E., Parker, Bernard F., Lussier, Daniel J., Garner, Mary E., Booth, Corwin H., Love, Jason B., & Arnold, John. Benzoquinonoid-bridged dinuclear actinide complexes. United States. doi:10.1039/c7dt02728a.
Hohloch, Stephan, Pankhurst, James R., Jaekel, Esther E., Parker, Bernard F., Lussier, Daniel J., Garner, Mary E., Booth, Corwin H., Love, Jason B., and Arnold, John. Wed . "Benzoquinonoid-bridged dinuclear actinide complexes". United States. doi:10.1039/c7dt02728a. https://www.osti.gov/servlets/purl/1493246.
@article{osti_1493246,
title = {Benzoquinonoid-bridged dinuclear actinide complexes},
author = {Hohloch, Stephan and Pankhurst, James R. and Jaekel, Esther E. and Parker, Bernard F. and Lussier, Daniel J. and Garner, Mary E. and Booth, Corwin H. and Love, Jason B. and Arnold, John},
abstractNote = {We report here the coordination chemistry of the tripodal tris[2-amido(2-pyridyl)ethyl]amine ligand, L, with thorium(IV) and uranium(IV). Using a salt-metathesis strategy from the potassium salt of this ligand, K3L, new actinide complexes were isolated, namely the dimeric thorium complex [ThCl(L)]2 (1) and the monomeric uranium complex UI(THF)(L) (2); under different crystallisation conditions, the dimeric uranium complex is also isolated, [UI(L)]2 (2-dimer). With the aim of studying electronic phenomena such as magnetic exchange between two actinide ions, we have synthesised the first examples of dinuclear, quinoid-bridged actinide complexes from dianionic 2,5-bis[2,6-(diisopropyl)anilide]-1,4-benzoquinone (QDipp) and 2,5-bis[2-(methoxy)anilide]-1,4-benzoquinone (QOMe) ligands. The resulting complexes are [Th(L)]2QDipp (3), [Th(THF)(L)]2QOMe (5) and [U(L)]2QOMe (6). The targeted [U(L)]2QDipp complex (4) could not be isolated. All isolated complexes have been characterised by spectroscopic methods and X-ray crystallography. The uranium(IV) complexes 2-dimer and 6 have been studied by SQUID magnetometry but indicate that there is negligible magnetic exchange between the two uranium(IV) ions. The reduced form of 6, [K(18-c-6)][6-] is unstable and highly sensitive, but X-ray crystallography indicates that it is a novel UIVUIV complex bridged by a quinoid-radical.},
doi = {10.1039/c7dt02728a},
journal = {Dalton Transactions},
number = 35,
volume = 46,
place = {United States},
year = {2017},
month = {8}
}

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Works referenced in this record:

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976


    Works referencing / citing this record:

    CCDC 1510089: Experimental Crystal Structure Determination: WECVUY : bis(μ-iodo)-bis(N,N',N''-[nitrilotri(ethane-2,1-diyl)]tri(pyridin-2-amino))-di-uranium(iv)
    dataset, October 2016

    • Hohloch, Stephan; Pankhurst, James R.; Jaekel, Esther E.
    • Cambridge Structural Database (CSD)
    • DOI: 10.5517/ccdc.csd.cc1mpck7