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Title: Synthesis, Structure, and Vibrational Properties of [Ph4P]2NpO2Cl4 and [Ph4P]2PuO2Cl4 Complexes

Abstract

In this paper, the synthesis, structure, and vibrational properties are presented for an isostructural series of Np(VI) and Pu(VI) complexes of the form [Ph4P]2AnO2Cl4, where An = Np(VI) or Pu(VI). The reported complexes are readily synthesized in ambient laboratory conditions, and their molecular structures were determined using single crystal X-ray diffraction. Their vibrational spectra were studied using a combination of Raman and FT-IR vibrational spectroscopies. Analysis of the vibrational spectra and force constants highlight the periodic properties associated with the actinide contraction and filling of the 5f electronic shells. Finally and additionally, we have assessed the utility of these complexes as conveniently synthesized starting materials for non-aqueous synthesis of transuranium molecules and materials.

Authors:
 [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1461426
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 6; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Schnaars, David D., and Wilson, Richard E. Synthesis, Structure, and Vibrational Properties of [Ph4P]2NpO2Cl4 and [Ph4P]2PuO2Cl4 Complexes. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.7b02382.
Schnaars, David D., & Wilson, Richard E. Synthesis, Structure, and Vibrational Properties of [Ph4P]2NpO2Cl4 and [Ph4P]2PuO2Cl4 Complexes. United States. https://doi.org/10.1021/acs.inorgchem.7b02382
Schnaars, David D., and Wilson, Richard E. Thu . "Synthesis, Structure, and Vibrational Properties of [Ph4P]2NpO2Cl4 and [Ph4P]2PuO2Cl4 Complexes". United States. https://doi.org/10.1021/acs.inorgchem.7b02382. https://www.osti.gov/servlets/purl/1461426.
@article{osti_1461426,
title = {Synthesis, Structure, and Vibrational Properties of [Ph4P]2NpO2Cl4 and [Ph4P]2PuO2Cl4 Complexes},
author = {Schnaars, David D. and Wilson, Richard E.},
abstractNote = {In this paper, the synthesis, structure, and vibrational properties are presented for an isostructural series of Np(VI) and Pu(VI) complexes of the form [Ph4P]2AnO2Cl4, where An = Np(VI) or Pu(VI). The reported complexes are readily synthesized in ambient laboratory conditions, and their molecular structures were determined using single crystal X-ray diffraction. Their vibrational spectra were studied using a combination of Raman and FT-IR vibrational spectroscopies. Analysis of the vibrational spectra and force constants highlight the periodic properties associated with the actinide contraction and filling of the 5f electronic shells. Finally and additionally, we have assessed the utility of these complexes as conveniently synthesized starting materials for non-aqueous synthesis of transuranium molecules and materials.},
doi = {10.1021/acs.inorgchem.7b02382},
journal = {Inorganic Chemistry},
number = 6,
volume = 57,
place = {United States},
year = {2018},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
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Citation Metrics:
Cited by: 6 works
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Figures / Tables:

Figure 1 Figure 1: Solid-state structures of [PPh4]2NpO2Cl4·2CH2Cl2 Np in gray, chlorine (green), oxygen (red), phosphorous (magenta), carbon (black). H atoms on the PPh4+ cation have been omitted for clarity.

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Works referenced in this record:

Covalency in f-element complexes
journal, January 2013

  • Neidig, Michael L.; Clark, David L.; Martin, Richard L.
  • Coordination Chemistry Reviews, Vol. 257, Issue 2
  • DOI: 10.1016/j.ccr.2012.04.029

Elucidating Protactinium Hydrolysis: The Relative Stabilities of PaO 2 (H 2 O) + and PaO(OH) 2 +
journal, July 2015


Covalency hinders AnO 2 (H 2 O) + → AnO(OH) 2 + isomerisation (An = Pa–Pu)
journal, January 2016


Reliable Potential Energy Surfaces for the Reactions of H 2 O with ThO 2 , PaO 2 + , UO 2 2+ , and UO 2 +
journal, November 2015

  • Vasiliu, Monica; Peterson, Kirk A.; Gibson, John K.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 46
  • DOI: 10.1021/acs.jpca.5b08618

Effect of spin-orbit coupling on the actinide dioxides AnO 2 (An=Th, Pa, U, Np, Pu, and Am): A screened hybrid density functional study
journal, October 2012

  • Wen, Xiao-Dong; Martin, Richard L.; Roy, Lindsay E.
  • The Journal of Chemical Physics, Vol. 137, Issue 15
  • DOI: 10.1063/1.4757615

Synthesis and Structure of (Ph 4 P) 2 MCl 6 (M = Ti, Zr, Hf, Th, U, Np, Pu)
journal, May 2012

  • Minasian, Stefan G.; Boland, Kevin S.; Feller, Russell K.
  • Inorganic Chemistry, Vol. 51, Issue 10
  • DOI: 10.1021/ic300179d

Curium(III) Borate Shows Coordination Environments of Both Plutonium(III) and Americium(III) Borates
journal, January 2012

  • Polinski, Matthew J.; Wang, Shuao; Alekseev, Evgeny V.
  • Angewandte Chemie International Edition, Vol. 51, Issue 8
  • DOI: 10.1002/anie.201107956

Structural and Vibrational Properties of U(VI)O 2 Cl 4 2- and Pu(VI)O 2 Cl 4 2- Complexes
journal, November 2013

  • Schnaars, David D.; Wilson, Richard E.
  • Inorganic Chemistry, Vol. 52, Issue 24
  • DOI: 10.1021/ic401991n

Lattice Solvent and Crystal Phase Effects on the Vibrational Spectra of UO 2 Cl 4 2–
journal, September 2014

  • Schnaars, David D.; Wilson, Richard E.
  • Inorganic Chemistry, Vol. 53, Issue 20
  • DOI: 10.1021/ic501553m

The unusual stability of [NpO2Cl4]2−: Synthesis and characterisation of [NpO2(DPPMO2)2Cl]2[NpO2Cl4] and [Ph3PNH2]2[NpO2Cl4]
journal, June 2010

  • Cornet, Stéphanie M.; Redmond, Michael P.; Collison, David
  • Comptes Rendus Chimie, Vol. 13, Issue 6-7
  • DOI: 10.1016/j.crci.2010.04.013

Synthesis and structure of ditetrabutylammonium tetrachlorodioxoneptunium(VI)
journal, November 2004

  • Wilkerson, Marianne P.; Dewey, Harry J.; Gordon, Pamela L.
  • Journal of Chemical Crystallography, Vol. 34, Issue 11
  • DOI: 10.1007/s10870-004-7657-9

Dicaesium tetrachloridodioxidoplutonate(VI)
journal, December 2007

  • Wilkerson, Marianne P.; Scott, Brian L.
  • Acta Crystallographica Section E Structure Reports Online, Vol. 64, Issue 1
  • DOI: 10.1107/S1600536807066354

Supramolecular Interactions in PuO 2 Cl 4 2– and PuCl 6 2– Complexes with Protonated Pyridines: Synthesis, Crystal Structures, and Raman Spectroscopy
journal, December 2013

  • Wilson, Richard E.; Schnaars, David D.; Andrews, Michael B.
  • Inorganic Chemistry, Vol. 53, Issue 1
  • DOI: 10.1021/ic4023294

The Reaction Chemistry of Plutonyl(VI) Chloride Complexes with Triphenyl Phosphineoxide and Triphenyl Phosphinimine
journal, October 2010

  • Berthon, Claude; Boubals, Nathalie; Charushnikova, Iraida A.
  • Inorganic Chemistry, Vol. 49, Issue 20
  • DOI: 10.1021/ic101251a

How to make weak hydrogen bonds less weak
journal, January 1998

  • Braga, Dario; Grepioni, Fabrizia
  • New Journal of Chemistry, Vol. 22, Issue 11
  • DOI: 10.1039/a806554c

Understanding the Behavior of Halogens as Hydrogen Bond Acceptors
journal, July 2001

  • Brammer, Lee; Bruton, Eric A.; Sherwood, Paul
  • Crystal Growth & Design, Vol. 1, Issue 4
  • DOI: 10.1021/cg015522k

Hydrogen-Bond Distances to Halide Ions in Organic and Organometallic Crystal Structures: Up-to-date Database Study
journal, August 1998


The Raman Scattering of Uranyl and Transuranium V, VI, and VII Ions
journal, March 1974


Theoretical Studies of the Properties and Solution Chemistry of AnO 2 2+ and AnO 2 + Aquo Complexes for An = U, Np, and Pu
journal, July 2000

  • Hay, P. Jeffrey; Martin, Richard L.; Schreckenbach, Georg
  • The Journal of Physical Chemistry A, Vol. 104, Issue 26
  • DOI: 10.1021/jp000519h

Infrared Spectra and Structure of Uranyl and Transuranium ( V ) and ( VI ) Ions in Aqueous Perchloric Acid Solution
journal, March 1953

  • Jones, Llewellyn H.; Penneman, Robert A.
  • The Journal of Chemical Physics, Vol. 21, Issue 3
  • DOI: 10.1063/1.1698941

The electronic structure of actinyl ions: V.
journal, June 1982


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


Ab Initio Quantum Chemical Calculations on Uranyl UO22+, Plutonyl PuO22+, and Their Nitrates and Sulfates
journal, June 1995

  • Craw, J. Simon; Vincent, Mark A.; Hillier, Ian H.
  • The Journal of Physical Chemistry, Vol. 99, Issue 25
  • DOI: 10.1021/j100025a019

An X-ray crystallographic, Raman, and infrared spectral study of crystalline potassium uranyl carbonate, K 4 UO 2 (CO 3 ) 3
journal, August 1980

  • Anderson, Anthony; Chieh, Chung; Irish, Donald E.
  • Canadian Journal of Chemistry, Vol. 58, Issue 16
  • DOI: 10.1139/v80-264

Synthesis and Structural Examination of Complexes of Am(IV) and Other Tetravalent Actinides with Lacunary Heteropolyanion α 2 -P 2 W 17 O 61 10−
journal, October 2009

  • Sokolova, Marina N.; Fedosseev, Alexander M.; Andreev, Grigory B.
  • Inorganic Chemistry, Vol. 48, Issue 19
  • DOI: 10.1021/ic900710c

Polymeric Structure of Oxalato-Bridged Complexes of Tetravalent Actinides Th, U, Np and Pu
journal, November 2011

  • Andreev, Grigory; Budantseva, Nina; Fedoseev, Aleksander
  • Inorganic Chemistry, Vol. 50, Issue 22
  • DOI: 10.1021/ic201313g

The Cambridge Structural Database: a quarter of a million crystal structures and rising
journal, May 2002


Transuranic Hybrid Materials: Crystallographic and Computational Metrics of Supramolecular Assembly
journal, July 2017

  • Surbella, Robert G.; Ducati, Lucas C.; Pellegrini, Kristi L.
  • Journal of the American Chemical Society, Vol. 139, Issue 31
  • DOI: 10.1021/jacs.7b05689

Organometallic Neptunium Chemistry
journal, August 2017


A Convenient Entry into Trivalent Actinide Chemistry: Synthesis and Characterization of AnI3(THF)4 and An[N(SiMe3)2]3 (An = U, Np, Pu)
journal, May 1994

  • Avens, Larry R.; Bott, Simon G.; Clark, David L.
  • Inorganic Chemistry, Vol. 33, Issue 10
  • DOI: 10.1021/ic00088a030

Low-Valent Molecular Plutonium Halide Complexes
journal, September 2008

  • Gaunt, Andrew J.; Reilly, Sean D.; Enriquez, Alejandro E.
  • Inorganic Chemistry, Vol. 47, Issue 18
  • DOI: 10.1021/ic8009139

Recent Developments in Synthesis and Structural Chemistry of Nonaqueous Actinide Complexes
journal, October 2012

  • Jones, Matthew B.; Gaunt, Andrew J.
  • Chemical Reviews, Vol. 113, Issue 2
  • DOI: 10.1021/cr300198m

Convenient access to the anhydrous thorium tetrachloride complexes ThCl4(DME)2, ThCl4(1,4-dioxane)2 and ThCl4(THF)3.5 using commercially available and inexpensive starting materials
journal, January 2010

  • Cantat, Thibault; Scott, Brian L.; Kiplinger, Jaqueline L.
  • Chemical Communications, Vol. 46, Issue 6
  • DOI: 10.1039/b923558b

Neptunium(vi) chain and neptunium(vi/v) mixed valence cluster complexes
journal, January 2009

  • Cornet, Stéphanie M.; Häller, L. Jonas L.; Sarsfield, Mark J.
  • Chemical Communications, Issue 8
  • DOI: 10.1039/b818973k

Optical and X-ray data on a group of isostructural uranium and plutonium compounds
journal, July 1952


An entry route into non-aqueous plutonyl coordination chemistry
journal, January 2007

  • Gaunt, Andrew J.; Reilly, Sean D.; Hayton, Trevor W.
  • Chemical Communications, Issue 16
  • DOI: 10.1039/b618577k

Works referencing / citing this record:

Impacts of hydrogen bonding interactions with Np( v / vi )O 2 Cl 4 complexes: vibrational spectroscopy, redox behavior, and computational analysis
journal, January 2020

  • Pyrch, Mikaela M.; Bjorklund, Jennifer L.; Williams, James M.
  • Dalton Transactions, Vol. 49, Issue 20
  • DOI: 10.1039/d0dt00848f

Actinyl-cation interactions: experimental and theoretical assessment of [Np( vi )O 2 Cl 4 ] 2− and [U( vi )O 2 Cl 4 ] 2− systems
journal, January 2019

  • Bjorklund, Jennifer L.; Pyrch, Mikaela M.; Basile, Madeline C.
  • Dalton Transactions, Vol. 48, Issue 24
  • DOI: 10.1039/c9dt01753d

Restricted Speciation and Supramolecular Assembly in the 5f Block
journal, July 2018

  • Carter, Korey P.; Surbella, Robert G.; Kalaj, Mark
  • Chemistry - A European Journal, Vol. 24, Issue 49
  • DOI: 10.1002/chem.201801044

Reductive activation of neptunyl and plutonyl oxo species with a hydroxypyridinone chelating ligand
journal, January 2018

  • Carter, Korey P.; Jian, Jiwen; Pyrch, Mikaela M.
  • Chemical Communications, Vol. 54, Issue 76
  • DOI: 10.1039/c8cc05626a

Exploring crown-ether functionalization on the stabilization of hexavalent neptunium
journal, January 2019

  • Pyrch, Mikaela M.; Williams, James M.; Forbes, Tori Z.
  • Chemical Communications, Vol. 55, Issue 63
  • DOI: 10.1039/c9cc04393d

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