Synthesis and spectroscopic characterization of actinyl(VI) tetrahalide coordination compounds containing 2, 2'-bipyridine

Pyrch, Mikaela M.; Williams, Jay M.; Kasperski, Maguire W.; Applegate, Lindsey C.; Forbes, Tori Z.

doi:10.1016/j.ica.2020.119628

Title: Synthesis and spectroscopic characterization of actinyl(VI) tetrahalide coordination compounds containing 2, 2'-bipyridine

Abstract

A series of three new actinide tetrahalide coordination compounds containing 2,2'-bipyridinium (H₂bpy) have been synthesized by room temperature evaporation and characterized via single crystal X-ray diffraction, Raman spectroscopy, and infrared spectroscopy. The solid-state compounds (Np1, U1, and U2) contain the AnO₂²⁺ cation coordinated to four halide (chloride or bromide) atoms to form the anionic tetrahalide molecular unit [AnO₂X₄]^2– (X = Cl, Br) and are charge balanced by the 2,2'-bipyridinium cations that engage in electrostatic interactions with the actinyl complex. Np1 (N₂C₁₀H₁₀)[NpO₂Cl₄] contains 2,2'-bipyridine in the cis conformation where both the nitrogen atoms are directed towards the [NpO₂Cl₄]^2– monomer. Within U1 (N₂C₁₀H₉)[UO₂Cl₄], the 2,2'-bipyridine is in a trans conformation, and found in the same orientation in the isomorphous structure U2 (N₂C₁₀H₉)[UO₂Br₄]. The compounds were further characterized by vibrational spectroscopy with specific interest in the actinyl cation. Raman spectroscopy provided information on the actinyl symmetric stretch (ν₁) whereas IR spectroscopy is used to determine the location of the asymmetric stretch (ν₃). Here, spectral similarities are observed between the two isomorphous structures, but slight variations across the series of structures are found to be associated with bipyridine bands in the various conformations. Additional analysis of these vibrational features in U1 and U2 providedmore »« less

Authors:

Pyrch, Mikaela M. ^[1]; Williams, Jay M. ^[1]; Kasperski, Maguire W. ^[1]; Applegate, Lindsey C. ^[1]; Forbes, Tori Z. ^[1]

University of Iowa, Iowa City, IA (United States)

Publication Date:: Thu Mar 26 00:00:00 EDT 2020

Research Org.:: Univ. of Iowa, Iowa City, IA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE

OSTI Identifier:: 1668737

Alternate Identifier(s):: OSTI ID: 1608071

Grant/Contract Number:: SC0013980

Resource Type:: Accepted Manuscript

Journal Name:: Inorganica Chimica Acta

Additional Journal Information:: Journal Volume: 508; Journal ID: ISSN 0020-1693

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Neptunium; coordination compounds; X-ray diffraction; Raman spectroscopy; crystallography; force constants; actinide complex; uranyl; neptunyl

Citation Formats


                    Pyrch, Mikaela M., Williams, Jay M., Kasperski, Maguire W., Applegate, Lindsey C., and Forbes, Tori Z. Synthesis and spectroscopic characterization of actinyl(VI) tetrahalide coordination compounds containing 2, 2'-bipyridine.  United States: N. p., 2020. 
Web.  doi:10.1016/j.ica.2020.119628.

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                    Pyrch, Mikaela M., Williams, Jay M., Kasperski, Maguire W., Applegate, Lindsey C., & Forbes, Tori Z. Synthesis and spectroscopic characterization of actinyl(VI) tetrahalide coordination compounds containing 2, 2'-bipyridine.  United States.  https://doi.org/10.1016/j.ica.2020.119628

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                    Pyrch, Mikaela M., Williams, Jay M., Kasperski, Maguire W., Applegate, Lindsey C., and Forbes, Tori Z. Thu .  
"Synthesis and spectroscopic characterization of actinyl(VI) tetrahalide coordination compounds containing 2, 2'-bipyridine".  United States.  https://doi.org/10.1016/j.ica.2020.119628.  https://www.osti.gov/servlets/purl/1668737.

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@article{osti_1668737,

  title        = {Synthesis and spectroscopic characterization of actinyl(VI) tetrahalide coordination compounds containing 2, 2'-bipyridine},

  author       = {Pyrch, Mikaela M. and Williams, Jay M. and Kasperski, Maguire W. and Applegate, Lindsey C. and Forbes, Tori Z.},

  abstractNote = {A series of three new actinide tetrahalide coordination compounds containing 2,2'-bipyridinium (H2bpy) have been synthesized by room temperature evaporation and characterized via single crystal X-ray diffraction, Raman spectroscopy, and infrared spectroscopy. The solid-state compounds (Np1, U1, and U2) contain the AnO22+ cation coordinated to four halide (chloride or bromide) atoms to form the anionic tetrahalide molecular unit [AnO2X4]2– (X = Cl, Br) and are charge balanced by the 2,2'-bipyridinium cations that engage in electrostatic interactions with the actinyl complex. Np1 (N2C10H10)[NpO2Cl4] contains 2,2'-bipyridine in the cis conformation where both the nitrogen atoms are directed towards the [NpO2Cl4]2– monomer. Within U1 (N2C10H9)[UO2Cl4], the 2,2'-bipyridine is in a trans conformation, and found in the same orientation in the isomorphous structure U2 (N2C10H9)[UO2Br4]. The compounds were further characterized by vibrational spectroscopy with specific interest in the actinyl cation. Raman spectroscopy provided information on the actinyl symmetric stretch (ν1) whereas IR spectroscopy is used to determine the location of the asymmetric stretch (ν3). Here, spectral similarities are observed between the two isomorphous structures, but slight variations across the series of structures are found to be associated with bipyridine bands in the various conformations. Additional analysis of these vibrational features in U1 and U2 provided information on the actinyl force constants, allowing insight into the relative uranyl bond strength that was compared to similar tetrahalide compounds.},

  doi          = {10.1016/j.ica.2020.119628},

  journal      = {Inorganica Chimica Acta},

  number       = ,

  volume       = 508,

  place        = {United States},

  year         = {Thu Mar 26 00:00:00 EDT 2020},

  month        = {Thu Mar 26 00:00:00 EDT 2020}

}

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Title: Synthesis and spectroscopic characterization of actinyl(VI) tetrahalide coordination compounds containing 2, 2'-bipyridine

Abstract

Citation Formats

Nuclear Energy and Uranium Resources journal, June 2007

Nuclear Fuel Cycle: Environmental Impact journal, April 2008

The Nuclear Fuel Cycle: A Role for Mineralogy and Geochemistry journal, December 2006

Geochemistry of the waste isolation pilot plant (WIPP) site, southestern New Mexico, U.S.A. journal, November 1992

Geochemistry of formation waters from the Wolfcamp and “Cline” shales: Insights into brine origin, reservoir connectivity, and fluid flow in the Permian Basin, USA journal, May 2016

Evolution of formation waters in the Permian Basin, United States: Late Permian evaporated seawater to Neogene meteoric water journal, March 2018

Preliminary Results of Laboratory Studies of Repository Chemistry for the Waste Isolation Pilot Plant journal, January 1990

The Expected Environment for Waste Packages in a Salt Repository journal, January 1983

Sensitivity of Solvation Environment to Oxidation State and Position in the Early Actinide Period journal, June 2015

Electronic Structure and Bonding in Actinyl Ions and their Analogs journal, May 2007

Neptunium redox speciation journal, January 2001

A Critical Evaluation of the Redox Properties of Uranium, Neptunium and Plutonium Ions in Acidic Aqueous Solutions journal, September 1999

Neptunium Diverges Sharply from Uranium and Plutonium in Crystalline Borate Matrixes: Insights into the Complex Behavior of the Early Actinides Relevant to Nuclear Waste Storage journal, January 2010

Solution and Solid-State Structural Chemistry of Actinide Hydrates and Their Hydrolysis and Condensation Products journal, October 2012

Uranyl Bearing Hybrid Materials: Synthesis, Speciation, and Solid-State Structures journal, August 2012

Aqueous uranium complexes. 2. Raman spectroscopic study of the complex formation of the dioxouranium(VI) ion with a variety of inorganic and organic ligands journal, December 1992

Probing the Electronic Structure and Chemical Bonding in Tricoordinate Uranyl Complexes UO 2 X 3 – (X = F, Cl, Br, I): Competition between Coulomb Repulsion and U–X Bonding journal, May 2013

Exploring the Effects of Reduction or Lewis Acid Coordination on the UO Bond of the Uranyl Moiety journal, April 2009

Bipyridine: The Most Widely Used Ligand. A Review of Molecules Comprising at Least Two 2,2‘-Bipyridine Units journal, October 2000

Conformation and Protonation of 2,2‘-Bipyridine and 4,4‘-Bipyridine in Acidic Aqueous Media and Acidic ZSM-5 Zeolites: A Raman Scattering Study journal, December 2001

A short history of SHELX journal, December 2007

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

Charge Transfer Vibronic Transitions in Uranyl Tetrachloride Compounds 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

The uranyl tetrachloride anion as a tecton in the assembly of U(VI) hybrid materials journal, January 2009

Supramolecular chemistry with uranyl tetrahalide ([UO2X4]2−) anions journal, June 2010

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

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

Chemical Speciation of Neptunium(VI) under Strongly Alkaline Conditions. Structure, Composition, and Oxo Ligand Exchange journal, June 2012

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

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

Impacts of oxo interactions within actinyl metal organic materials: highlight on thermal expansion behaviour journal, January 2018

Conformers, Energetics, and Basicity of 2,2‘-Bipyridine journal, January 1996

ULTRAVIOLET SPECTRA AND STRUCTURES OF 2,2'-BIPYRIDINE AND 2,2',2″-TERPYRIDINE IN AQUEOUS SOLUTION 1 journal, October 1960

Conformations of 2,2′-bipyridine in acidic media journal, July 1987

Torsional profiles of protonated and metal-coordinated 2,2′-bipyridine journal, October 2004

Crystal structure of di-(2,2?-pyridylpyridinium)tetrachlorodioxouranate(VI) journal, April 1988

Crystal and molecular structure of di-(2,2?-pyridylpyridinium)tetrachlorodioxouranate (VI) journal, April 1987

Detection and identification of solids, surfaces, and solutions of uranium using vibrational spectroscopy journal, November 2018

Raman spectroscopy of neptunyl and plutonyl in aqueous solutions: hydrolysis of Np(VI) and Pu(VI) and disproportionation of Pu(V) journal, February 1984

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

Mid-, far-infrared and raman spectra of uranyl complexes in aqueous solutions journal, January 1984

Probing the Nature of Chemical Bonding in Uranyl(VI) Complexes with Quantum Chemical Methods journal, November 2012

Use of Charge-Assisted Hydrogen Bonding in the Supramolecular Assembly of Hybrid Uranyl Materials journal, January 2014

Vibrational assignments of crystalline waters in some uranyl halide complexes journal, January 1979

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

IR and Raman spectra of A 2,2′-bipyridine single crystal: internal modes journal, November 1979

Crystallization in Ionic Liquids: Synthesis, Properties, and Polymorphs of Uranyl Salts journal, October 2014

The low frequency infrared and Raman spectroscopic studies of some uranyl complexes: the deformation frequency of the uranyl ion journal, October 1970

Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms journal, August 2017

Nuclear Energy and Uranium Resources
journal, June 2007

Nuclear Fuel Cycle: Environmental Impact
journal, April 2008

The Nuclear Fuel Cycle: A Role for Mineralogy and Geochemistry
journal, December 2006

Geochemistry of the waste isolation pilot plant (WIPP) site, southestern New Mexico, U.S.A.
journal, November 1992

Geochemistry of formation waters from the Wolfcamp and “Cline” shales: Insights into brine origin, reservoir connectivity, and fluid flow in the Permian Basin, USA
journal, May 2016

Evolution of formation waters in the Permian Basin, United States: Late Permian evaporated seawater to Neogene meteoric water
journal, March 2018

Preliminary Results of Laboratory Studies of Repository Chemistry for the Waste Isolation Pilot Plant
journal, January 1990

The Expected Environment for Waste Packages in a Salt Repository
journal, January 1983

Sensitivity of Solvation Environment to Oxidation State and Position in the Early Actinide Period
journal, June 2015

Electronic Structure and Bonding in Actinyl Ions and their Analogs
journal, May 2007

Neptunium redox speciation
journal, January 2001

A Critical Evaluation of the Redox Properties of Uranium, Neptunium and Plutonium Ions in Acidic Aqueous Solutions
journal, September 1999

Neptunium Diverges Sharply from Uranium and Plutonium in Crystalline Borate Matrixes: Insights into the Complex Behavior of the Early Actinides Relevant to Nuclear Waste Storage
journal, January 2010

Solution and Solid-State Structural Chemistry of Actinide Hydrates and Their Hydrolysis and Condensation Products
journal, October 2012

Uranyl Bearing Hybrid Materials: Synthesis, Speciation, and Solid-State Structures
journal, August 2012

Aqueous uranium complexes. 2. Raman spectroscopic study of the complex formation of the dioxouranium(VI) ion with a variety of inorganic and organic ligands
journal, December 1992

Probing the Electronic Structure and Chemical Bonding in Tricoordinate Uranyl Complexes UO ₂ X ₃ ^– (X = F, Cl, Br, I): Competition between Coulomb Repulsion and U–X Bonding
journal, May 2013

Exploring the Effects of Reduction or Lewis Acid Coordination on the UO Bond of the Uranyl Moiety
journal, April 2009

Bipyridine: The Most Widely Used Ligand. A Review of Molecules Comprising at Least Two 2,2‘-Bipyridine Units
journal, October 2000

Conformation and Protonation of 2,2‘-Bipyridine and 4,4‘-Bipyridine in Acidic Aqueous Media and Acidic ZSM-5 Zeolites: A Raman Scattering Study
journal, December 2001

A short history of SHELX
journal, December 2007

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

Charge Transfer Vibronic Transitions in Uranyl Tetrachloride Compounds
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

The uranyl tetrachloride anion as a tecton in the assembly of U(VI) hybrid materials
journal, January 2009

Supramolecular chemistry with uranyl tetrahalide ([UO2X4]2−) anions
journal, June 2010

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

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

Chemical Speciation of Neptunium(VI) under Strongly Alkaline Conditions. Structure, Composition, and Oxo Ligand Exchange
journal, June 2012

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

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

Impacts of oxo interactions within actinyl metal organic materials: highlight on thermal expansion behaviour
journal, January 2018

Conformers, Energetics, and Basicity of 2,2‘-Bipyridine
journal, January 1996

ULTRAVIOLET SPECTRA AND STRUCTURES OF 2,2'-BIPYRIDINE AND 2,2',2″-TERPYRIDINE IN AQUEOUS SOLUTION ¹
journal, October 1960

Conformations of 2,2′-bipyridine in acidic media
journal, July 1987

Torsional profiles of protonated and metal-coordinated 2,2′-bipyridine
journal, October 2004

Crystal structure of di-(2,2?-pyridylpyridinium)tetrachlorodioxouranate(VI)
journal, April 1988

Crystal and molecular structure of di-(2,2?-pyridylpyridinium)tetrachlorodioxouranate (VI)
journal, April 1987

Detection and identification of solids, surfaces, and solutions of uranium using vibrational spectroscopy
journal, November 2018

Raman spectroscopy of neptunyl and plutonyl in aqueous solutions: hydrolysis of Np(VI) and Pu(VI) and disproportionation of Pu(V)
journal, February 1984

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

Mid-, far-infrared and raman spectra of uranyl complexes in aqueous solutions
journal, January 1984

Probing the Nature of Chemical Bonding in Uranyl(VI) Complexes with Quantum Chemical Methods
journal, November 2012

Use of Charge-Assisted Hydrogen Bonding in the Supramolecular Assembly of Hybrid Uranyl Materials
journal, January 2014

Vibrational assignments of crystalline waters in some uranyl halide complexes
journal, January 1979

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

IR and Raman spectra of A 2,2′-bipyridine single crystal: internal modes
journal, November 1979

Crystallization in Ionic Liquids: Synthesis, Properties, and Polymorphs of Uranyl Salts
journal, October 2014

The low frequency infrared and Raman spectroscopic studies of some uranyl complexes: the deformation frequency of the uranyl ion
journal, October 1970

Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms
journal, August 2017