Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Impacts of hydrogen bonding interactions with Np(v/vi)O2Cl4 complexes: vibrational spectroscopy, redox behavior, and computational analysis

Journal Article · · Dalton Transactions
DOI:https://doi.org/10.1039/d0dt00848f· OSTI ID:1668739
 [1];  [2];  [2];  [2];  [2];  [2];  [2]
  1. University of Iowa, Iowa City, IA (United States); University of Iowa
  2. University of Iowa, Iowa City, IA (United States)
+ Show Author Affiliations
The neptunyl (Np(V)O2+/Np(VI)O22+) cation is the dominant form of 237Np in acidic aqueous solutions and the stability of the Np(V) and Np(VI) species is driven by the specific chemical constituents present in the system. Hydrogen bonding with the oxo group may impact the stability of these species, but there is limited understanding of how these intermolecular interactions influence the behavior of both solution and solid-state species. In the current study, we systematically evaluate the interactions between the neptunyl tetrachloride species and hydrogen donors in coordination complexes and in the related aqueous solutions. Both Np(V) compounds (N2C4H12)2[Np(V)O2Cl4]Cl (Np(V)pipz) and (NOC4H10)3[Np(V)O2Cl4] (Np(V)morph) exhibit directional hydrogen bonding to the neptunyl oxo group while Np(VI) compounds (NC5H6)2[Np(VI)O2Cl4] (Np(VI)pyr) and (NOC4H10)4[Np(VI)O2Cl4]·2Cl (Np(VI)morph) assemble via halogen interactions. Here, the Raman spectra of the solid-state phases indicate the activation of vibrational bands when there is asymmetry of the neptunyl bond, while these spectral features are not observed within the related solution phase spectra. Density functional theory calculations of the Np(V)pipz system suggest that activation of the ν3 asymmetric stretch and other combination modes lead to additional complexity within the solid-state spectra. Electrochemical analyses of complexes in the solution phases are consistent with the results of the crystallization experiments as the voltammetric potentials of Np(V)/Np(VI) complexes in the presence of protonated heterocycles differ from the potentials of pure Np(V) and may correlate with the hydrogen bonding interactions.
Research Organization:
University of Iowa, Iowa City, IA (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
SC0013980
OSTI ID:
1668739
Alternate ID(s):
OSTI ID: 1617757
Journal Information:
Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 20 Vol. 49; ISSN 1477-9226
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (49)

Cation—Cation Interaction in Crystalline Actinide Compounds journal June 2004
Charge-Assisted Hydrogen-Bonding and Crystallization Effects within U VI Glycine Compounds : Charge-Assisted Hydrogen-Bonding and Crystallization Effects within U journal April 2017
Pentavalent Neptunyl ([O≡Np≡O]+) Cation–Cation Interactions in Aqueous/Polar Organic Mixed-Solvent Media journal June 2017
Separation and preconcentration of actinides from acidic media by extraction chromatography journal September 1993
“Cation-cation” complexes of pentavalent actinides—I journal January 1979
The analytical chemistry of neptunium journal January 1974
Surface enhanced raman spectroscopy of pyridine, pyridinium ions and chloride ions adsorbed on the silver electrode journal June 1984
Solid state vibrational spectroscopy of some piperidinium and morpholinium salts of tin(IV), antimony(III) and bismuth(III) halide complexes journal January 1978
Voltammetric determination of neptunium at the glassy carbon electrode journal August 1968
Cyclic voltammetry of Pu and Np in nitric acid media journal November 1971
The infra-red and Raman spectra of piperazine journal March 1962
Detection and identification of solids, surfaces, and solutions of uranium using vibrational spectroscopy journal November 2018
Probing of different conformations of piperazine using Raman spectroscopy journal June 2014
The unusual stability of [NpO2Cl4]2−: Synthesis and characterisation of [NpO2(DPPMO2)2Cl]2[NpO2Cl4] and [Ph3PNH2]2[NpO2Cl4] journal June 2010
Separation of plutonium and neptunium from uranium by N,N-dimethyl-3-oxa-glutaramic acid (DMOGA) as a complexant in the PUREX process journal October 2015
Reduction behavior of neptunium(V) at a gold or platinum electrode during controlled potential electrolysis and procedures for electrochemical preparations of neptunium(IV) and (III) journal March 2010
Sensitivity of Solvation Environment to Oxidation State and Position in the Early Actinide Period journal June 2015
Series of Hydrated Heterometallic Uranyl-Cobalt(II) Coordination Polymers with Aromatic Polycarboxylate Ligands: Formation of U═O—Co Bonding upon Dehydration Process journal September 2016
A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO 2 ·M] 4+ Cation–Cation Complexes journal April 2017
Synthesis, Structure, and Vibrational Properties of [Ph 4 P] 2 NpO 2 Cl 4 and [Ph 4 P] 2 PuO 2 Cl 4 Complexes journal March 2018
Peculiarities of the Supramolecular Assembly of Tetraethylammonium and 3-Bromopropionate Ions in Uranyl, Neptunyl, and Plutonyl Coordination Compounds journal October 2019
Use of Charge-Assisted Hydrogen Bonding in the Supramolecular Assembly of Hybrid Uranyl Materials journal January 2014
Coordination Trends in Alkali Metal Crown Ether Uranyl Halide Complexes:  The Series [A(Crown)] 2 [UO 2 X 4 ] Where A = Li, Na, K and X = Cl, Br journal July 2001
Electrochemical and Complexation Behavior of Neptunium in Aqueous Perchlorate and Nitrate Solutions journal September 2008
Complex Formation and Molecular Structure of Neptunyl(VI) and -(V) Acetates journal September 2009
Relativistic and correlation effects for element 105 (hahnium, Ha): a comparative study of M and MO (M = Nb, Ta, Ha) using energy-adjusted ab initio pseudopotentials journal June 1993
How Strong Is the C α −H···OC Hydrogen Bond? journal May 2000
Transuranic Hybrid Materials: Crystallographic and Computational Metrics of Supramolecular Assembly journal July 2017
Electronic Structure and Spectra of Actinyl Ions journal April 2001
Electronic Structure and Bonding in Actinyl Ions and their Analogs journal May 2007
Ion association with tetra-n-alkylammonium cations stabilizes higher-oxidation-state neptunium dioxocations journal January 2019
Taking a snapshot of the triplet excited state of an OLED organometallic luminophore using X-rays journal May 2020
Mechanisms of neptunium redox reactions in nitric acid solutions journal January 2017
Impacts of oxo interactions within actinyl metal organic materials: highlight on thermal expansion behaviour journal January 2018
Exploring crown-ether functionalization on the stabilization of hexavalent neptunium journal January 2019
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
COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient journal January 1993
On the nature of hydrogen bonds: an overview on computational studies and a word about patterns journal January 2007
Valence basis sets for relativistic energy-consistent small-core actinide pseudopotentials journal January 2003
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Cation–cation interaction in crystalline actinide compounds journal January 2004
Spectroscopic studies of vibrational relaxation and chemical exchange broadening in hydrogen bonded systems. IV. Analysis of the isotropic Raman bands of pyridine/water system journal June 1995
Simulation of Neptunium Extraction in an Advanced PUREX Process—Model Improvement journal January 2017
A short history of SHELX journal December 2007
XSEDE: Accelerating Scientific Discovery journal September 2014
A Critical Evaluation of the Redox Properties of Uranium, Neptunium and Plutonium Ions in Acidic Aqueous Solutions journal September 1999
Neptunium redox speciation journal January 2001
Neptunium(V) disproportionation and cation–cation interactions in TBP/kerosene solvent journal January 2007
Recent Developments in the Purex Process for Nuclear Fuel Reprocessing: Complexant Based Stripping for Uranium/Plutonium Separation journal December 2005

Similar Records

Impacts of Oxo Interactions on Np(V) Crown Ether Complexes
Journal Article · Sun May 06 20:00:00 EDT 2018 · Inorganic Chemistry · OSTI ID:1668716
Assessing subtle variations in the actinyl oxo reactivity through characterization of neptunyl complexes. Final Report
Technical Report · Tue Mar 23 00:00:00 EDT 2021 · OSTI ID:1772240
Actinyl-cation interactions: experimental and theoretical assessment of [Np(vi)O2Cl4]2– and [U(vi)O2Cl4]2– systems
Journal Article · Mon May 20 20:00:00 EDT 2019 · Dalton Transactions · OSTI ID:1668729

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Neptunium
density functional theory
electrochemistry
hydrogen bonding
oxo interactions