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

The following gas-phase uranyl/12-crown-4 (12C4) complexes were synthesized by electrospray ionization: [UO 2(12C4) 2] 2+and [UO 2(12C4) 2(OH)] +. Collision-induced dissociation (CID) of the dication resulted in [UO 2(12C4-H)] +(12C4-H is a 12C4 that has lost one H), which spontaneously adds water to yield [UO 2(12C4-H)(H 2O)] +. The latter has the same composition as complex [UO 2(12C4)(OH)] + produced by CID of [UO 2(12C4) 2(OH)] + but exhibits different reactivity with water. The postulated structures as isomeric [UO 2(12C4-H)(H 2O)] + and [UO 2(12C4)(OH)] + were confirmed by comparison of infrared multiphoton dissociation (IRMPD) spectra with computed spectra. The structure of [UO 2(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:
 [1] ;  [2] ;  [3] ;  [4] ; ORCiD logo [5] ; ORCiD logo [5] ;  [6] ; ORCiD logo [3] ; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. 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
  3. Beijing (China). Dept. of Chemistry and Key Lab. of Organic Optoelectronics & Molecular Engineering of Ministry of Education
  4. Duquesne Univ., Pittsburgh, PA (United States). Dept. of Chemistry and Biochemistry
  5. Radboud Univ., Nijmegen (Netherlands). Inst. for Molecules and Materials, FELIX Lab.
  6. 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:
Grant/Contract Number:
AC02-05CH11231
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)
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1461137

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., Web. doi:10.1021/acs.inorgchem.8b00306.
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. doi:10.1021/acs.inorgchem.8b00306.
Jian, Jiwen, Hu, Shu-Xian, Li, Wan-Lu, van Stipdonk, Michael J., Martens, Jonathan, Berden, Giel, Oomens, Jos, Li, Jun, and Gibson, John K.. 2018. "Uranyl/12-crown-4 Ether Complexes and Derivatives: Structural Characterization and Isomeric Differentiation". United States. doi:10.1021/acs.inorgchem.8b00306.
@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 = {2018},
month = {3}
}