title: Organometallic neptunium(III) complexes.
abstract: 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 U(III) 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 Np(IV). Here we report the synthesis of three new Np(III) organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that Np(III) complexes could act as single-molecule magnets, and that the lower oxidation state of Np(II) is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key Np(III) orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements.
authors.affiliation: EaStCHEM School of Chemistry, University of Edinburgh, The King's Buildings, Edinburgh EH9 3FJ, UK.|European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), Postfach 2340, D-76125 Karlsruhe, Germany.
authors.forename: Michał S
authors.initials: MS
authors.lastname: Dutkiewicz
authors.affiliation: EaStCHEM School of Chemistry, University of Edinburgh, The King's Buildings, Edinburgh EH9 3FJ, UK.
authors.forename: Joy H
authors.initials: JH
authors.lastname: Farnaby
authors.affiliation: European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), Postfach 2340, D-76125 Karlsruhe, Germany.
authors.forename: Christos
authors.initials: C
authors.lastname: Apostolidis
authors.affiliation: European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), Postfach 2340, D-76125 Karlsruhe, Germany.
authors.forename: Eric
authors.initials: E
authors.lastname: Colineau
authors.affiliation: European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), Postfach 2340, D-76125 Karlsruhe, Germany.
authors.forename: Olaf
authors.initials: O
authors.lastname: Walter
authors.affiliation: European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), Postfach 2340, D-76125 Karlsruhe, Germany.
authors.forename: Nicola
authors.initials: N
authors.lastname: Magnani
authors.affiliation: School of Physical Sciences (Chemistry), University of Tasmania, Private Bag 75, Hobart, Tasmania 7001, Australia.
authors.forename: Michael G
authors.initials: MG
authors.lastname: Gardiner
authors.affiliation: EaStCHEM School of Chemistry, University of Edinburgh, The King's Buildings, Edinburgh EH9 3FJ, UK.
authors.forename: Jason B
authors.initials: JB
authors.lastname: Love
authors.affiliation: Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK.|School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK.
authors.forename: Nikolas
authors.identifier: 0000-0003-0293-5742
authors.initials: N
authors.lastname: Kaltsoyannis
authors.affiliation: European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), Postfach 2340, D-76125 Karlsruhe, Germany.
authors.forename: Roberto
authors.initials: R
authors.lastname: Caciuffo
authors.affiliation: EaStCHEM School of Chemistry, University of Edinburgh, The King's Buildings, Edinburgh EH9 3FJ, UK.
authors.forename: Polly L
authors.identifier: 0000-0001-6410-5838
authors.initials: PL
authors.lastname: Arnold