Organometallic neptunium(III) complexes

Dutkiewicz, M. S. et al. (2016) Organometallic neptunium(III) complexes. Nature Chemistry, 8(8), pp. 797-802. (doi: 10.1038/nchem.2520) (PMID:27442286)

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Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal–ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on UIII and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to NpIV. Here we report the synthesis of three new NpIII organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that NpIII complexes could act as single-molecule magnets, and that the lower oxidation state of NpII is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key NpIII orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements.

Item Type:Articles
Additional Information:Experiments were supported by the European FP7 TALISMAN project, under contract with the European Commission, the JRC ITU USERLAB programme, the University of Edinburgh, European Cooperation in Science and Technology action CM1006 and the Engineering and Physical Sciences Research Council EP/H004823/1 and EP/M010554/1. M.S.D. acknowledges the European Commission for support in the frame of the Training and Mobility of Researchers programme.
Glasgow Author(s) Enlighten ID:Farnaby, Dr Joy
Authors: Dutkiewicz, M. S., Farnaby, J. H., Apostolidis, C., Colineau, E., Walter, O., Magnani, N., Gardiner, M. G., Love, J. B., Kaltsoyannis, N., Caciuffo, R., and Arnold, P. L.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Nature Chemistry
Publisher:Nature Publishing Group
ISSN (Online):1755-4349
Published Online:23 May 2016
Copyright Holders:Copyright © 2016 Macmillan Publishers Limited
First Published:First published in Nature Chemistry 8(8): 797-802
Publisher Policy:Reproduced in accordance with the publisher copyright policy

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