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

Journal Article · · Inorganic Chemistry
 [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
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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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1461426
Journal Information:
Inorganic Chemistry, Vol. 57, Issue 6; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 18 works
Citation information provided by
Web of Science

References (40)

Covalency in f-element complexes journal January 2013
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
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
Synthesis and Structure of (Ph 4 P) 2 MCl 6 (M = Ti, Zr, Hf, Th, U, Np, Pu) journal May 2012
Curium(III) Borate Shows Coordination Environments of Both Plutonium(III) and Americium(III) Borates journal January 2012
Structural and Vibrational Properties of U(VI)O 2 Cl 4 2- and Pu(VI)O 2 Cl 4 2- Complexes journal November 2013
Lattice Solvent and Crystal Phase Effects on the Vibrational Spectra of UO 2 Cl 4 2– journal September 2014
The unusual stability of [NpO2Cl4]2−: Synthesis and characterisation of [NpO2(DPPMO2)2Cl]2[NpO2Cl4] and [Ph3PNH2]2[NpO2Cl4] journal June 2010
Crystal structure and spectroscopic measurements of room temperature intra-5f fluorescence of Cs2Np(VI)O2Cl4 journal October 2007
Synthesis and structure of ditetrabutylammonium tetrachlorodioxoneptunium(VI) journal November 2004
Dicaesium tetrachloridodioxidoplutonate(VI) journal December 2007
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
The Reaction Chemistry of Plutonyl(VI) Chloride Complexes with Triphenyl Phosphineoxide and Triphenyl Phosphinimine † journal October 2010
How to make weak hydrogen bonds less weak journal January 1998
Understanding the Behavior of Halogens as Hydrogen Bond Acceptors journal July 2001
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
Infrared Spectra and Structure of Uranyl and Transuranium ( V ) and ( VI ) Ions in Aqueous Perchloric Acid Solution journal March 1953
Raman spectroscopy of neptunyl and plutonyl ions in aqueous solution: hydrolysis of neptunium(VI) and plutonium(VI) and disproportionation of plutonium(V) journal June 1984
The electronic structure of actinyl ions: V. journal June 1982
Infrared Spectra and Structure of the Crystalline Sodium Acetate Complexes of U(VI), Np(VI), Pu(VI), and Am(VI). A Comparison of Metal‐Oxygen Bond Distance and Bond Force Constant in this Series journal November 1955
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
An X-ray crystallographic, Raman, and infrared spectral study of crystalline potassium uranyl carbonate, K 4 UO 2 (CO 3 ) 3 journal August 1980
Bonding Trends Traversing the Tetravalent Actinide Series: Synthesis, Structural, and Computational Analysis of An IV ( Ar acnac) 4 Complexes (An = Th, U, Np, Pu; Ar acnac = Ar N C(Ph)CHC(Ph) O ; Ar = 3,5- t Bu 2 C 6 H 3 ) journal July 2012
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
Polymeric Structure of Oxalato-Bridged Complexes of Tetravalent Actinides Th, U, Np and Pu journal November 2011
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
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
Low-Valent Molecular Plutonium Halide Complexes journal September 2008
Recent Developments in Synthesis and Structural Chemistry of Nonaqueous Actinide Complexes journal October 2012
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
Neptunium(vi) chain and neptunium(vi/v) mixed valence cluster complexes journal January 2009
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

Cited By (2)

Impacts of hydrogen bonding interactions with Np( v / vi )O 2 Cl 4 complexes: vibrational spectroscopy, redox behavior, and computational analysis journal January 2020
Restricted Speciation and Supramolecular Assembly in the 5f Block journal July 2018

Linked Research (5)

Figures / Tables (6)

Figure 1(p. 23)figure Figure 1
Figure 2(p. 24)figure Figure 2
Figure 3(p. 25)figure Figure 3
Table 1(p. 27)table Table 1
Table 2(p. 28)table Table 2
Table 3(p. 29)table Table 3

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