Organometallic neptunium(III) complexes

Michał S. Dutkiewicz; Joy H. Farnaby; Christos Apostolidis; Eric Colineau; Olaf  Walter; Nicola  Magnani; Michael G. Gardiner; Jason B. Love; Nikolas Kaltsoyannis; Roberto Caciuffo; Polly L. Arnold

doi:10.1038/nchem.2520

Organometallic neptunium(III) complexes

Michał S. Dutkiewicz, Joy H. Farnaby, Christos Apostolidis, Eric Colineau, Olaf Walter, Nicola Magnani, Michael G. Gardiner, Jason B. Love, Nikolas Kaltsoyannis, Roberto Caciuffo, Polly L. Arnold

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Abstract

Studies of transuranic organometallic complexes provide particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium AnIII ions and their lighter lanthanide LnIII counterparts are of fundamental importance for effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on UIII with 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 a range of new NpIII organometallics, and characterize their molecular and electronic structures. These studies suggest that the lower oxidation state of NpII is chemically accessible, and that NpIII complexes could act as single molecule magnets. Significant d- and f-electron contributions to key NpIII orbitals are found in comparison with lanthanide analogues, showing that fundamental Np organometallic chemistry can provide new insight into f-element behaviour.

Original language	English
Pages (from-to)	797–802
Journal	Nature Chemistry
Volume	8
DOIs	https://doi.org/10.1038/nchem.2520
Publication status	Published - 23 May 2016

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Np2Lar_NC_ms_REV_AAVAccepted author manuscript, 7.92 MB

CCDC 1423269: Experimental Crystal Structure Determination
Dutkiewicz, M. S. (Contributor), Farnaby, J. H. (Contributor), Apostolidis, C. (Contributor), Walter, O. (Contributor), Magnani, N. (Contributor), Gardiner, M. G. (Contributor), Love, J. B. (Contributor), Kaltsoyannis, N. (Contributor), Caciuffo, R. (Contributor) & Arnold, P. L. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1js0x7, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1js0x7&sid=DataCite
Dataset
CCDC 1423267: Experimental Crystal Structure Determination
Dutkiewicz, M. S. (Contributor), Farnaby, J. H. (Contributor), Apostolidis, C. (Contributor), Walter, O. (Contributor), Magnani, N. (Contributor), Gardiner, M. G. (Contributor), Love, J. B. (Contributor), Kaltsoyannis, N. (Contributor), Caciuffo, R. (Contributor) & Arnold, P. L. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1js0v5, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1js0v5&sid=DataCite
Dataset
CCDC 1423268: Experimental Crystal Structure Determination
Dutkiewicz, M. S. (Contributor), Farnaby, J. H. (Contributor), Apostolidis, C. (Contributor), Walter, O. (Contributor), Magnani, N. (Contributor), Gardiner, M. G. (Contributor), Love, J. B. (Contributor), Kaltsoyannis, N. (Contributor), Caciuffo, R. (Contributor) & Arnold, P. L. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2017
DOI: 10.5517/ccdc.csd.cc1js0w6, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1js0w6&sid=DataCite
Dataset

Cite this

@article{6245a1c8a0f740a1879d9bf2b4cd4ae4,

title = "Organometallic neptunium(III) complexes",

abstract = "Studies of transuranic organometallic complexes provide particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium AnIII ions and their lighter lanthanide LnIII counterparts are of fundamental importance for effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on UIII with 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 a range of new NpIII organometallics, and characterize their molecular and electronic structures. These studies suggest that the lower oxidation state of NpII is chemically accessible, and that NpIII complexes could act as single molecule magnets. Significant d- and f-electron contributions to key NpIII orbitals are found in comparison with lanthanide analogues, showing that fundamental Np organometallic chemistry can provide new insight into f-element behaviour.",

author = "Dutkiewicz, {Micha{\l} S.} and Farnaby, {Joy H.} and Christos Apostolidis and Eric Colineau and Olaf Walter and Nicola Magnani and Gardiner, {Michael G.} and Love, {Jason B.} and Nikolas Kaltsoyannis and Roberto Caciuffo and Arnold, {Polly L.}",

year = "2016",

month = may,

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doi = "10.1038/nchem.2520",

language = "English",

volume = "8",

pages = "797–802",

journal = "Nature Chemistry",

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T1 - Organometallic neptunium(III) complexes

AU - Dutkiewicz, Michał S.

AU - Farnaby, Joy H.

AU - Apostolidis, Christos

AU - Colineau, Eric

AU - Walter, Olaf

AU - Magnani, Nicola

AU - Gardiner, Michael G.

AU - Love, Jason B.

AU - Kaltsoyannis, Nikolas

AU - Caciuffo, Roberto

AU - Arnold, Polly L.

PY - 2016/5/23

Y1 - 2016/5/23

N2 - Studies of transuranic organometallic complexes provide particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium AnIII ions and their lighter lanthanide LnIII counterparts are of fundamental importance for effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on UIII with 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 a range of new NpIII organometallics, and characterize their molecular and electronic structures. These studies suggest that the lower oxidation state of NpII is chemically accessible, and that NpIII complexes could act as single molecule magnets. Significant d- and f-electron contributions to key NpIII orbitals are found in comparison with lanthanide analogues, showing that fundamental Np organometallic chemistry can provide new insight into f-element behaviour.

AB - Studies of transuranic organometallic complexes provide particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium AnIII ions and their lighter lanthanide LnIII counterparts are of fundamental importance for effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on UIII with 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 a range of new NpIII organometallics, and characterize their molecular and electronic structures. These studies suggest that the lower oxidation state of NpII is chemically accessible, and that NpIII complexes could act as single molecule magnets. Significant d- and f-electron contributions to key NpIII orbitals are found in comparison with lanthanide analogues, showing that fundamental Np organometallic chemistry can provide new insight into f-element behaviour.

U2 - 10.1038/nchem.2520

DO - 10.1038/nchem.2520

M3 - Article

SN - 1755-4330

VL - 8

SP - 797

EP - 802

JO - Nature Chemistry

JF - Nature Chemistry

ER -

Organometallic neptunium(III) complexes

Abstract

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Datasets

CCDC 1423269: Experimental Crystal Structure Determination

CCDC 1423267: Experimental Crystal Structure Determination

CCDC 1423268: Experimental Crystal Structure Determination

Cite this