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Title: Activation of Water by Pentavalent Actinide Dioxide Cations: Characteristic Curium Revealed by a Reactivity Turn after Americium

Abstract

Swapping of an oxygen atom of water with that of a pentavalent actinide dioxide cation, AnO 2 + also called an “actinyl”, requires activation of an An–O bond. It was previously found that such oxo exchange in the gas phase occurs for the first two actinyls, PaO 2 + and UO 2 +, but not the next two, NpO 2 + and PuO 2 +. The An–O bond dissociation energies (BDEs) decrease from PaO 2 + to PuO 2 +, such that the observation of a parallel decrease in the An–O bond reactivity is intriguing. To elucidate oxo exchange, we here extend experimental studies to AmO 2 +, americyl(V), and CmO 2 +, curyl(V), which were produced in remarkable abundance by electrospray ionization of Am 3+ and Cm 3+ solutions. Like other AnO 2 +, americyl(V) and curyl(V) adsorb up to four H 2O molecules to form tetrahydrates AnO 2(H 2O) 4 + with the actinide hexacoordinated by oxygen atoms. It was found that AmO 2 + does not oxo-exchange, whereas CmO 2 + does, establishing a “turn” to increasing the reactivity from americyl to curyl, which validates computational predictions. Because oxo exchange occurs via conversion of an actinyl(V) hydrate,more » AnO 2(H 2O) +, to an actinide(V) hydroxide, AnO(OH) 2 +, it reflects the propensity for actinyl(V) hydrolysis: PaO 2 + hydrolyzes and oxo-exchanges most easily, despite the fact that it has the highest BDE of all AnO 2 +. A reexamination of the computational results for actinyl(V) oxo exchange reveals distinctive properties and chemistry of curyl(V) species, particularly CmO(OH) 2 +.« less

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of Alabama, Tuscaloosa, AL (United States)
  3. Washington State Univ., Pullman, WA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1596108
Alternate Identifier(s):
OSTI ID: 1597719
Grant/Contract Number:  
SC00085019; AC02-05CH1123; SC0018921; AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 58; Journal Issue: 20; 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; Solvates; Energy; Anions; Hydrolysis; Molecules

Citation Formats

Jian, Tian, Dau, Phuong Diem, Shuh, David K., Vasiliu, Monica, Dixon, David A., Peterson, Kirk A., and Gibson, John K. Activation of Water by Pentavalent Actinide Dioxide Cations: Characteristic Curium Revealed by a Reactivity Turn after Americium. United States: N. p., 2019. Web. doi:10.1021/acs.inorgchem.9b01997.
Jian, Tian, Dau, Phuong Diem, Shuh, David K., Vasiliu, Monica, Dixon, David A., Peterson, Kirk A., & Gibson, John K. Activation of Water by Pentavalent Actinide Dioxide Cations: Characteristic Curium Revealed by a Reactivity Turn after Americium. United States. doi:10.1021/acs.inorgchem.9b01997.
Jian, Tian, Dau, Phuong Diem, Shuh, David K., Vasiliu, Monica, Dixon, David A., Peterson, Kirk A., and Gibson, John K. Thu . "Activation of Water by Pentavalent Actinide Dioxide Cations: Characteristic Curium Revealed by a Reactivity Turn after Americium". United States. doi:10.1021/acs.inorgchem.9b01997.
@article{osti_1596108,
title = {Activation of Water by Pentavalent Actinide Dioxide Cations: Characteristic Curium Revealed by a Reactivity Turn after Americium},
author = {Jian, Tian and Dau, Phuong Diem and Shuh, David K. and Vasiliu, Monica and Dixon, David A. and Peterson, Kirk A. and Gibson, John K.},
abstractNote = {Swapping of an oxygen atom of water with that of a pentavalent actinide dioxide cation, AnO2+ also called an “actinyl”, requires activation of an An–O bond. It was previously found that such oxo exchange in the gas phase occurs for the first two actinyls, PaO2+ and UO2+, but not the next two, NpO2+ and PuO2+. The An–O bond dissociation energies (BDEs) decrease from PaO2+ to PuO2+, such that the observation of a parallel decrease in the An–O bond reactivity is intriguing. To elucidate oxo exchange, we here extend experimental studies to AmO2+, americyl(V), and CmO2+, curyl(V), which were produced in remarkable abundance by electrospray ionization of Am3+ and Cm3+ solutions. Like other AnO2+, americyl(V) and curyl(V) adsorb up to four H2O molecules to form tetrahydrates AnO2(H2O)4+ with the actinide hexacoordinated by oxygen atoms. It was found that AmO2+ does not oxo-exchange, whereas CmO2+ does, establishing a “turn” to increasing the reactivity from americyl to curyl, which validates computational predictions. Because oxo exchange occurs via conversion of an actinyl(V) hydrate, AnO2(H2O)+, to an actinide(V) hydroxide, AnO(OH)2+, it reflects the propensity for actinyl(V) hydrolysis: PaO2+ hydrolyzes and oxo-exchanges most easily, despite the fact that it has the highest BDE of all AnO2+. A reexamination of the computational results for actinyl(V) oxo exchange reveals distinctive properties and chemistry of curyl(V) species, particularly CmO(OH)2+.},
doi = {10.1021/acs.inorgchem.9b01997},
journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 20,
volume = 58,
place = {United States},
year = {2019},
month = {9}
}

Journal Article:
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