The crystal and coordination chemistry of neptunium in all its oxidation states: An expanded structural hierarchy of neptunium compounds

Gilson, Sara E.; Burns, Peter C.

doi:10.1016/j.ccr.2021.213994

Title: The crystal and coordination chemistry of neptunium in all its oxidation states: An expanded structural hierarchy of neptunium compounds

Journal Article · Sat Jun 05 00:00:00 EDT 2021 · Coordination Chemistry Reviews

DOI:https://doi.org/10.1016/j.ccr.2021.213994· OSTI ID:1976915

Gilson, Sara E. ^[1];

^[1]

University of Notre Dame, IN (United States)

We report structures of 388 neptunium-bearing crystal structures are sorted into an expanded structural hierarchy and examined. The majority of structures contain Np(V) (149), Np(VI) (99), or Np(IV) (91) whereas structures containing Np(II), Np(III), Np(VII), or more than one oxidation state are rare. Coordination geometry of Np(V) and Np(VI) compounds is dominated by the approximately linear neptunyl cation. Actinyl–actinyl interactions (AAIs) are most prevalent in Np(V) compounds and are observed in 48% of these extended structures. Prismatic coordination geometries are commonly observed in Np(IV) compounds. Np(III) organometallic complexes display a variety of coordination modes. Coordination chemistry of Np(VII) compounds is dominated by the tetra-oxido core. Updated average bond length values are provided for Np(IV), Np(V), Np(VI), and Np(VII) compounds and updated bond valence parameters for Np(IV) are reported. A graphical notation system for neptunyl structures coordinated by organic ligands was developed to facilitate discussion and identify similarities between neptunyl compounds coordinated by oxyanions and neptunyl compounds coordinated by organic ligands.

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Research Organization:: University of Notre Dame, IN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-07ER15880

OSTI ID:: 1976915

Alternate ID(s):: OSTI ID: 1815048

Journal Information:: Coordination Chemistry Reviews, Vol. 445, Issue C; ISSN 0010-8545

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Structural Role of Isonicotinic Acid in U(VI), Np(VI), and Pu(VI) Complexes with TcO ₄ ^– , ReO ₄ ^– , and ClO ₄ ^– Ions Budantseva, Nina; Andreev, Grigory; Fedoseev, Aleksander Inorganic Chemistry, Vol. 56, Issue 20 https://doi.org/10.1021/acs.inorgchem.7b01611	journal	September 2017
Synthesis and properties of actinide dimolybdate complexes M2[AnO2(MoO4)2]·H2O (M = Rb, Cs; An = Np, Pu) Budantseva, N. A.; Grigor’ev, M. S.; Ivanova, A. G. Radiochemistry, Vol. 58, Issue 2 https://doi.org/10.1134/S1066362216020016	journal	March 2016
In Situ Hydrothermal Reduction of Neptunium(VI) as a Route to Neptunium(IV) Phosphonates Bray, Travis H.; Nelson, Anna-Gay D.; Jin, Geng Bang Inorganic Chemistry, Vol. 46, Issue 26 https://doi.org/10.1021/ic702136h	journal	December 2007
Synthesis, Structure, and Vibrational Properties of [Ph ₄ P] ₂ NpO ₂ Cl ₄ and [Ph ₄ P] ₂ PuO ₂ Cl ₄ Complexes Schnaars, David D.; Wilson, Richard E. Inorganic Chemistry, Vol. 57, Issue 6 https://doi.org/10.1021/acs.inorgchem.7b02382	journal	March 2018
The Crystal Chemistry of Sulfate Minerals Hawthorne, F. C.; Krivovichev, S. V.; Burns, P. C. Reviews in Mineralogy and Geochemistry, Vol. 40, Issue 1 https://doi.org/10.2138/rmg.2000.40.1	journal	January 2000
Synthesis and Structure of the First Transuranium Crown Ether Inclusion Complex: [NpO2([18]Crown-6)]ClO4 Clark, David L.; Keogh, D. Webster; Palmer, Phillip D. Angewandte Chemie International Edition, Vol. 37, Issue 1-2 https://doi.org/10.1002/(SICI)1521-3773(19980202)37:1/2<164::AID-ANIE164>3.0.CO;2-X	journal	February 1998
Hexaphyrin(1.0.1.0.0.0): An Expanded Porphyrin Ligand for the Actinide Cations Uranyl (UO22+) and Neptunyl (NpO2+) Sessler, Jonathan L.; Seidel, Daniel; Vivian, Anne E. Angewandte Chemie International Edition, Vol. 40, Issue 3 https://doi.org/10.1002/1521-3773(20010202)40:3<591::AID-ANIE591>3.0.CO;2-0	journal	January 2001

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