Uranyl/12-crown-4 Ether Complexes and Derivatives: Structural Characterization and Isomeric Differentiation

Jian, Jiwen; Hu, Shu-Xian; Li, Wan-Lu; van Stipdonk, Michael J.; Martens, Jonathan; Berden, Giel; Oomens, Jos; Li, Jun; Gibson, John K.

doi:10.1021/acs.inorgchem.8b00306

Title: Uranyl/12-crown-4 Ether Complexes and Derivatives: Structural Characterization and Isomeric Differentiation

Abstract

The following gas-phase uranyl/12-crown-4 (12C4) complexes were synthesized by electrospray ionization: [UO₂(12C4)₂]²⁺and [UO₂(12C4)₂(OH)]⁺. Collision-induced dissociation (CID) of the dication resulted in [UO₂(12C4-H)]⁺(12C4-H is a 12C4 that has lost one H), which spontaneously adds water to yield [UO₂(12C4-H)(H₂O)]⁺. The latter has the same composition as complex [UO₂(12C4)(OH)]⁺ produced by CID of [UO₂(12C4)₂(OH)]⁺ but exhibits different reactivity with water. The postulated structures as isomeric [UO₂(12C4-H)(H₂O)]⁺ and [UO₂(12C4)(OH)]⁺ were confirmed by comparison of infrared multiphoton dissociation (IRMPD) spectra with computed spectra. The structure of [UO₂(12C4-H)]⁺ corresponds to cleavage of a C-O bond in the 12C4 ring, with formation of a discrete U-O_eq bond and equatorial coordination by three intact ether moieties. Comparison of IRMPD and computed IR spectra furthermore enabled assignment of the structures of the other complexes. Theoretical studies of the chemical bonding features of the complexes provide an understanding of their stabilities and reactivities. Finally, the results reveal bonding and structures of the uranyl/12C4 complexes and demonstrate the synthesis and identification of two different isomers of gas-phase uranyl coordination complexes.

Authors:

Jian, Jiwen ^[1]; Hu, Shu-Xian ^[2]; Li, Wan-Lu ^[3]; van Stipdonk, Michael J. ^[4];

^[5];

^[5]; Oomens, Jos ^[6];

^[3];

^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Beijing Computational Science Research Center, Beijing (China); Tsinghua Univ., Beijing (China). Dept. of Chemistry and Key Lab. of Organic Optoelectronics & Molecular Engineering of Ministry of Education
Beijing (China). Dept. of Chemistry and Key Lab. of Organic Optoelectronics & Molecular Engineering of Ministry of Education
Duquesne Univ., Pittsburgh, PA (United States). Dept. of Chemistry and Biochemistry
Radboud Univ., Nijmegen (Netherlands). Inst. for Molecules and Materials, FELIX Lab.
Radboud Univ., Nijmegen (Netherlands). Inst. for Molecules and Materials, FELIX Lab.; Univ. of Amsterdam (Netherlands). Van‘t Hoff Inst. for Molecular Sciences (HIMS)

Publication Date:: Tue Mar 20 00:00:00 EDT 2018

Research Org.:: Energy Frontier Research Centers (EFRC) (United States). Center for Actinide Science & Technology (CAST); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

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

OSTI Identifier:: 1461137

Grant/Contract Number:: AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: Inorganic Chemistry

Additional Journal Information:: Journal Volume: 57; Journal Issue: 7; Journal ID: ISSN 0020-1669

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Jian, Jiwen, Hu, Shu-Xian, Li, Wan-Lu, van Stipdonk, Michael J., Martens, Jonathan, Berden, Giel, Oomens, Jos, Li, Jun, and Gibson, John K. Uranyl/12-crown-4 Ether Complexes and Derivatives: Structural Characterization and Isomeric Differentiation.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.inorgchem.8b00306.

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                    Jian, Jiwen, Hu, Shu-Xian, Li, Wan-Lu, van Stipdonk, Michael J., Martens, Jonathan, Berden, Giel, Oomens, Jos, Li, Jun, & Gibson, John K. Uranyl/12-crown-4 Ether Complexes and Derivatives: Structural Characterization and Isomeric Differentiation.  United States.  https://doi.org/10.1021/acs.inorgchem.8b00306

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                    Jian, Jiwen, Hu, Shu-Xian, Li, Wan-Lu, van Stipdonk, Michael J., Martens, Jonathan, Berden, Giel, Oomens, Jos, Li, Jun, and Gibson, John K. Tue .  
"Uranyl/12-crown-4 Ether Complexes and Derivatives: Structural Characterization and Isomeric Differentiation".  United States.  https://doi.org/10.1021/acs.inorgchem.8b00306.  https://www.osti.gov/servlets/purl/1461137.

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@article{osti_1461137,

  title        = {Uranyl/12-crown-4 Ether Complexes and Derivatives: Structural Characterization and Isomeric Differentiation},

  author       = {Jian, Jiwen and Hu, Shu-Xian and Li, Wan-Lu and van Stipdonk, Michael J. and Martens, Jonathan and Berden, Giel and Oomens, Jos and Li, Jun and Gibson, John K.},

  abstractNote = {The following gas-phase uranyl/12-crown-4 (12C4) complexes were synthesized by electrospray ionization: [UO2(12C4)2]2+and [UO2(12C4)2(OH)]+. Collision-induced dissociation (CID) of the dication resulted in [UO2(12C4-H)]+(12C4-H is a 12C4 that has lost one H), which spontaneously adds water to yield [UO2(12C4-H)(H2O)]+. The latter has the same composition as complex [UO2(12C4)(OH)]+ produced by CID of [UO2(12C4)2(OH)]+ but exhibits different reactivity with water. The postulated structures as isomeric [UO2(12C4-H)(H2O)]+ and [UO2(12C4)(OH)]+ were confirmed by comparison of infrared multiphoton dissociation (IRMPD) spectra with computed spectra. The structure of [UO2(12C4-H)]+ corresponds to cleavage of a C-O bond in the 12C4 ring, with formation of a discrete U-Oeq bond and equatorial coordination by three intact ether moieties. Comparison of IRMPD and computed IR spectra furthermore enabled assignment of the structures of the other complexes. Theoretical studies of the chemical bonding features of the complexes provide an understanding of their stabilities and reactivities. Finally, the results reveal bonding and structures of the uranyl/12C4 complexes and demonstrate the synthesis and identification of two different isomers of gas-phase uranyl coordination complexes.},

  doi          = {10.1021/acs.inorgchem.8b00306},

  journal      = {Inorganic Chemistry},

  number       = 7,

  volume       = 57,

  place        = {United States},

  year         = {Tue Mar 20 00:00:00 EDT 2018},

  month        = {Tue Mar 20 00:00:00 EDT 2018}

}

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Influence of Background H{sub 2}O on the Collision-Induced Dissociation Products Generated from [UO{sub 2}NO{sub 3}]{sup +}

Journal Article Stipdonk, Michael J. Van, ; Iacovino, Anna ; Tatosian, Irena - Journal of the American Society for Mass Spectrometry

Developing a comprehensive understanding of the reactivity of uranium-containing species remains an important goal in areas ranging from the development of nuclear fuel processing methods to studies of the migration and fate of the element in the environment. Electrospray ionization (ESI) is an effective way to generate gas-phase complexes containing uranium for subsequent studies of intrinsic structure and reactivity. Recent experiments by our group have demonstrated that the relatively low levels of residual H{sub 2}O in a 2-D, linear ion trap (LIT) make it possible to examine fragmentation pathways and reactions not observed in earlier studies conducted with 3-D ionmore »« less
https://doi.org/10.1007/S13361-018-1947-5

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Title: Uranyl/12-crown-4 Ether Complexes and Derivatives: Structural Characterization and Isomeric Differentiation

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Citation Formats

Design and Synthesis of Macrocyclic Ligands and Their Complexes of Lanthanides and Actinides journal, March 1995

Rational Design of Sequestering Agents for Plutonium and Other Actinides journal, November 2003

Use of Soft Heterocyclic N-Donor Ligands To Separate Actinides and Lanthanides journal, June 2012

Crown Ethers: Sensors for Ions and Molecular Scaffolds for Materials and Biological Models journal, May 2004

Macrocyclic Polyethers and Their Complexes journal, January 1972

Infrared Spectroscopy of Divalent Zinc and Cadmium Crown Ether Systems journal, June 2011

Synthesis and structural elucidation of novel uranyl-crown ether compounds isolated from nitric, hydrochloric, sulfuric, and acetic acids journal, June 1991

f-Element–crown ether complexes. Part 9. The role of solvent hydrogen bonding: synthesis and crystal structure of aquatetrachlorotris(ethanol)thorium( IV )–1,4,7,10,13,16-hexaoxacyclo-octadecane–water (1/1/1) journal, January 1988

f-Element/crown ether complexes, 11. Preparation and structural characterization of [UO2(OH2)5] [ClO4]2�3(15-crown-5)�CH3CN and [UO2(OH2)5] [ClO4]2�2(18-crown-6)�2 CH3CN�H2O journal, October 1987

Synthesis and structure of the 1:1 uranyl nitrate tetrahydrate-18-crown-6 compound, UO2(NO3)2(H2O)2.2H2O.(18-crown-6). Noncoordination of uranyl by the crown ether journal, October 1976

Crystal structures of the dicyclohexyl-(18-crown-6) uranyl perchlorate complex and of its hydrolysis product journal, January 1984

EXAFS analysis of aqueous and acetonitrile solutions of UO2-trilate with crown-ethers and aza-crowns. Crystals structures of the inclusion complexes UO2(18-crown-6)(CF3SO3)2 and UO2(dicyclohexyl-18-crown-6)(CF3SO3)2 journal, June 1994

Spectroscopic properties of uranyl crown ether complexes in non-aqueous solvents journal, January 2004

Synthesis and Structure of the First Transuranium Crown Ether Inclusion Complex: [NpO2([18]Crown-6)]ClO4 journal, February 1998

Crown Ether Inclusion Complexes of the Early Actinide Elements, [AnO 2 (18-crown-6)] n + , An = U, Np, Pu and n = 1, 2: A Relativistic Density Functional Study journal, March 2008

Crown Ether Complexes of Uranyl, Neptunyl, and Plutonyl: Hydration Differentiates Inclusion versus Outer Coordination journal, May 2014

Electronic structure and characterization of a uranyl di-15-crown-5 complex with an unprecedented sandwich structure journal, January 2016

Gas-Phase Uranyl, Neptunyl, and Plutonyl: Hydration and Oxidation Studied by Experiment and Theory journal, June 2012

A Tetrapositive Metal Ion in the Gas Phase: Thorium(IV) Coordinated by Neutral Tridentate Ligands journal, May 2013

Gas-Phase Coordination Complexes of UVIO 2 2+ , NpVIO 2 2+ , and PuVIO 2 2+ with Dimethylformamide journal, August 2011

The Free-Electron-Laser user facility FELIX journal, January 1995

Infrared ion spectroscopy in a modified quadrupole ion trap mass spectrometer at the FELIX free electron laser laboratory journal, October 2016

Structural identification of electron transfer dissociation products in mass spectrometry using infrared ion spectroscopy journal, June 2016

Vibrational study of isolated 18-crown-6 ether complexes with alkaline-earth metal cations journal, December 2011

Tweezer-like Complexes of Crown Ethers with Divalent Metals: Probing Cation-Size-Dependent Conformations by Vibrational Spectroscopy in the Gas Phase journal, January 2012

Synthesis and Hydrolysis of Uranyl, Neptunyl, and Plutonyl Gas-Phase Complexes Exhibiting Discrete Actinide–Carbon Bonds journal, April 2016

Density‐functional thermochemistry. III. The role of exact exchange journal, April 1993

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal, January 1988

Valence basis sets for relativistic energy-consistent small-core actinide pseudopotentials journal, January 2003

Segmented contraction scheme for small-core actinide pseudopotential basis sets journal, March 2004

Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18 journal, May 1980

Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions journal, May 1992

Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon journal, January 1993

Atomic reference energies for density functional calculations journal, February 1997

Relativistic regular two‐component Hamiltonians journal, September 1993

Geometry optimizations in the zero order regular approximation for relativistic effects journal, May 1999

Optimized Slater-type basis sets for the elements 1-118 journal, May 2003

Charge, bond order and valence in the AB initio SCF theory journal, May 1983

Valency. I. A quantum chemical definition and properties journal, September 1983

Bond Multiplicity in Transition-Metal Complexes: Applications of Two-Electron Valence Indices journal, August 2008

Bonded-atom fragments for describing molecular charge densities journal, January 1977

The Carbon−Lithium Electron Pair Bond in (CH 3 Li) n ( n = 1, 2, 4) journal, January 1996

A charge analysis derived from an atomic multipole expansion journal, January 2000

Electronic Population Analysis on LCAO–MO Molecular Wave Functions. I journal, October 1955

A theoretical study of the ethylene-metal bond in complexes between copper(1+), silver(1+), gold(1+), platinum(0) or platinum(2+) and ethylene, based on the Hartree-Fock-Slater transition-state method journal, June 1979

Two-electron valence indices from the Kohn-Sham orbitals journal, January 1997

A simple measure of electron localization in atomic and molecular systems journal, May 1990

Vibrational and Electronic Spectroscopy of Acenaphthylene and Its Cation journal, February 2003

An Evaluation of Harmonic Vibrational Frequency Scale Factors journal, November 2007

Vibrational spectra of discrete UO22+ halide complexes in the gas phase journal, November 2010

Infrared Multiphoton Dissociation Spectroscopy of a Gas-Phase Complex of Uranyl and 3-Oxa-Glutaramide: An Extreme Red-Shift of the [O═U═O] 2+ Asymmetric Stretch journal, March 2015

Novel unidentate co-ordination of a crown ether and of a polyethylene glycol to uranium(VI) journal, January 1989

Synthesis and Structural Characterization of the Monodentate 12-Crown-4 And Hexaethylene Glycol Complexes of Uranium(VI): [UO 2 Cl 2 (OH 2 ) 2 (12-CROWN-4)].12-Crown-4 And UO 2 Cl 2 (OH 2 ) 2 (Hexaethylene Glycol) journal, January 1992

Design and Synthesis of Macrocyclic Ligands and Their Complexes of Lanthanides and Actinides
journal, March 1995

Rational Design of Sequestering Agents for Plutonium and Other Actinides
journal, November 2003

Use of Soft Heterocyclic N-Donor Ligands To Separate Actinides and Lanthanides
journal, June 2012

Crown Ethers: Sensors for Ions and Molecular Scaffolds for Materials and Biological Models
journal, May 2004

Macrocyclic Polyethers and Their Complexes
journal, January 1972

Infrared Spectroscopy of Divalent Zinc and Cadmium Crown Ether Systems
journal, June 2011

Synthesis and structural elucidation of novel uranyl-crown ether compounds isolated from nitric, hydrochloric, sulfuric, and acetic acids
journal, June 1991

f-Element–crown ether complexes. Part 9. The role of solvent hydrogen bonding: synthesis and crystal structure of aquatetrachlorotris(ethanol)thorium( IV )–1,4,7,10,13,16-hexaoxacyclo-octadecane–water (1/1/1)
journal, January 1988

f-Element/crown ether complexes, 11. Preparation and structural characterization of [UO2(OH2)5] [ClO4]2�3(15-crown-5)�CH3CN and [UO2(OH2)5] [ClO4]2�2(18-crown-6)�2 CH3CN�H2O
journal, October 1987

Synthesis and structure of the 1:1 uranyl nitrate tetrahydrate-18-crown-6 compound, UO2(NO3)2(H2O)2.2H2O.(18-crown-6). Noncoordination of uranyl by the crown ether
journal, October 1976

Crystal structures of the dicyclohexyl-(18-crown-6) uranyl perchlorate complex and of its hydrolysis product
journal, January 1984

EXAFS analysis of aqueous and acetonitrile solutions of UO2-trilate with crown-ethers and aza-crowns. Crystals structures of the inclusion complexes UO2(18-crown-6)(CF3SO3)2 and UO2(dicyclohexyl-18-crown-6)(CF3SO3)2
journal, June 1994

Spectroscopic properties of uranyl crown ether complexes in non-aqueous solvents
journal, January 2004

Synthesis and Structure of the First Transuranium Crown Ether Inclusion Complex: [NpO2([18]Crown-6)]ClO4
journal, February 1998

Crown Ether Inclusion Complexes of the Early Actinide Elements, [AnO ₂ (18-crown-6)] ^{n +} , An = U, Np, Pu and n = 1, 2: A Relativistic Density Functional Study
journal, March 2008

Crown Ether Complexes of Uranyl, Neptunyl, and Plutonyl: Hydration Differentiates Inclusion versus Outer Coordination
journal, May 2014

Electronic structure and characterization of a uranyl di-15-crown-5 complex with an unprecedented sandwich structure
journal, January 2016

Gas-Phase Uranyl, Neptunyl, and Plutonyl: Hydration and Oxidation Studied by Experiment and Theory
journal, June 2012

A Tetrapositive Metal Ion in the Gas Phase: Thorium(IV) Coordinated by Neutral Tridentate Ligands
journal, May 2013

Gas-Phase Coordination Complexes of UVIO 2 2+ , NpVIO 2 2+ , and PuVIO 2 2+ with Dimethylformamide
journal, August 2011

The Free-Electron-Laser user facility FELIX
journal, January 1995

Infrared ion spectroscopy in a modified quadrupole ion trap mass spectrometer at the FELIX free electron laser laboratory
journal, October 2016

Structural identification of electron transfer dissociation products in mass spectrometry using infrared ion spectroscopy
journal, June 2016

Vibrational study of isolated 18-crown-6 ether complexes with alkaline-earth metal cations
journal, December 2011

Tweezer-like Complexes of Crown Ethers with Divalent Metals: Probing Cation-Size-Dependent Conformations by Vibrational Spectroscopy in the Gas Phase
journal, January 2012

Synthesis and Hydrolysis of Uranyl, Neptunyl, and Plutonyl Gas-Phase Complexes Exhibiting Discrete Actinide–Carbon Bonds
journal, April 2016

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988

Valence basis sets for relativistic energy-consistent small-core actinide pseudopotentials
journal, January 2003

Segmented contraction scheme for small-core actinide pseudopotential basis sets
journal, March 2004

Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18
journal, May 1980

Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
journal, May 1992

Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon
journal, January 1993

Atomic reference energies for density functional calculations
journal, February 1997

Relativistic regular two‐component Hamiltonians
journal, September 1993

Geometry optimizations in the zero order regular approximation for relativistic effects
journal, May 1999

Optimized Slater-type basis sets for the elements 1-118
journal, May 2003

Charge, bond order and valence in the AB initio SCF theory
journal, May 1983

Valency. I. A quantum chemical definition and properties
journal, September 1983

Bond Multiplicity in Transition-Metal Complexes: Applications of Two-Electron Valence Indices
journal, August 2008

Bonded-atom fragments for describing molecular charge densities
journal, January 1977

The Carbon−Lithium Electron Pair Bond in (CH ₃ Li) _n ( n = 1, 2, 4)
journal, January 1996

A charge analysis derived from an atomic multipole expansion
journal, January 2000

Electronic Population Analysis on LCAO–MO Molecular Wave Functions. I
journal, October 1955

A theoretical study of the ethylene-metal bond in complexes between copper(1+), silver(1+), gold(1+), platinum(0) or platinum(2+) and ethylene, based on the Hartree-Fock-Slater transition-state method
journal, June 1979

Two-electron valence indices from the Kohn-Sham orbitals
journal, January 1997

A simple measure of electron localization in atomic and molecular systems
journal, May 1990

Vibrational and Electronic Spectroscopy of Acenaphthylene and Its Cation
journal, February 2003

An Evaluation of Harmonic Vibrational Frequency Scale Factors
journal, November 2007

Vibrational spectra of discrete UO22+ halide complexes in the gas phase
journal, November 2010

Infrared Multiphoton Dissociation Spectroscopy of a Gas-Phase Complex of Uranyl and 3-Oxa-Glutaramide: An Extreme Red-Shift of the [O═U═O] ²⁺ Asymmetric Stretch
journal, March 2015

Novel unidentate co-ordination of a crown ether and of a polyethylene glycol to uranium(VI)
journal, January 1989

Synthesis and Structural Characterization of the Monodentate 12-Crown-4 And Hexaethylene Glycol Complexes of Uranium(VI): [UO ₂ Cl ₂ (OH ₂ ) ₂ (12-CROWN-4)].12-Crown-4 And UO ₂ Cl ₂ (OH ₂ ) ₂ (Hexaethylene Glycol)
journal, January 1992