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Title: Ditechnetium heptoxide revisited: Solid-state, gas-phase, and theoretical studies

Abstract

Ditechnetium heptoxide was synthesized from the oxidation of TcO2 with O2 at 450 °C and characterized by single-crystal X-ray diffraction, electron-impact mass spectrometry (EI-MS), and theoretical methods. Refinement of the structure at 100 K indicates that Tc2O7 crystallizes as a molecular solid in the orthorhombic space group Pbca [a = 7.312(3) Å, b = 5.562(2) Å, c = 13.707(5) Å, and V = 557.5(3) Å3]. The Tc2O7 molecule can be described as corner-sharing TcO4 tetrahedron [Tc---Tc = 3.698(1) Å and Tc-OBri-Tc = 180.0°]. The EI-MS spectrum of Tc2O7 consists of both mononuclear and dinuclear species. The main dinuclear species in the gas-phase are Tc2O7 (100%) and Tc2O5 (56%), while the main mononuclear species are TcO3 (33.9%) and TcO2 (42.8%). The difference in the relative intensities of the M2O5 (M = Tc, Re) fragments (1.7% for Re) indicates that these group 7 elements exhibit different gas-phase chemistry. The solid-state structure of Tc2O7 was investigated by density functional theory methods. The optimized structure of the Tc2O7 molecule is in good agreement with the experimental one. Simulations indicate that the more favorable geometry for the Tc2O7 molecule in the gas-phase is bent (Tc-OBri-Tc = 156.5°), while a linear geometry (Tc-OBri-Tc = 180.0°) ismore » favored in the solid-state.« less

Authors:
 [1];  [2];  [1];  [1];  [2];  [2];  [1];  [1];  [2];  [3];  [1]
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  1. Univ. of Nevada, Las Vegas, NV (United States)
  2. Univ. of Zurich, Zurich (Switzerland)
  3. Univ. of Nevada, Las Vegas, NV (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States); Univ. of California, Berkeley, CA (United States). Nuclear Science and Security Consortium
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1339618
Alternate Identifier(s):
OSTI ID: 1405177
Grant/Contract Number:  
AC02-06CH11357; NA0003180
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 55; 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

Citation Formats

Childs, Bradley C., Braband, Henrik, Lawler, Keith, Mast, Daniel S., Bigler, Laurent, Stalder, Urs, Forster, Paul M., Czerwinski, Kenneth R., Alberto, Roger, Sattelberger, Alfred P., and Poineau, Frederic. Ditechnetium heptoxide revisited: Solid-state, gas-phase, and theoretical studies. United States: N. p., 2016. Web. doi:10.1021/acs.inorgchem.6b01683.
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Childs, Bradley C., Braband, Henrik, Lawler, Keith, Mast, Daniel S., Bigler, Laurent, Stalder, Urs, Forster, Paul M., Czerwinski, Kenneth R., Alberto, Roger, Sattelberger, Alfred P., & Poineau, Frederic. Ditechnetium heptoxide revisited: Solid-state, gas-phase, and theoretical studies. United States. https://doi.org/10.1021/acs.inorgchem.6b01683
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Childs, Bradley C., Braband, Henrik, Lawler, Keith, Mast, Daniel S., Bigler, Laurent, Stalder, Urs, Forster, Paul M., Czerwinski, Kenneth R., Alberto, Roger, Sattelberger, Alfred P., and Poineau, Frederic. Tue . "Ditechnetium heptoxide revisited: Solid-state, gas-phase, and theoretical studies". United States. https://doi.org/10.1021/acs.inorgchem.6b01683. https://www.osti.gov/servlets/purl/1339618.
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@article{osti_1339618,
title = {Ditechnetium heptoxide revisited: Solid-state, gas-phase, and theoretical studies},
author = {Childs, Bradley C. and Braband, Henrik and Lawler, Keith and Mast, Daniel S. and Bigler, Laurent and Stalder, Urs and Forster, Paul M. and Czerwinski, Kenneth R. and Alberto, Roger and Sattelberger, Alfred P. and Poineau, Frederic},
abstractNote = {Ditechnetium heptoxide was synthesized from the oxidation of TcO2 with O2 at 450 °C and characterized by single-crystal X-ray diffraction, electron-impact mass spectrometry (EI-MS), and theoretical methods. Refinement of the structure at 100 K indicates that Tc2O7 crystallizes as a molecular solid in the orthorhombic space group Pbca [a = 7.312(3) Å, b = 5.562(2) Å, c = 13.707(5) Å, and V = 557.5(3) Å3]. The Tc2O7 molecule can be described as corner-sharing TcO4 tetrahedron [Tc---Tc = 3.698(1) Å and Tc-OBri-Tc = 180.0°]. The EI-MS spectrum of Tc2O7 consists of both mononuclear and dinuclear species. The main dinuclear species in the gas-phase are Tc2O7 (100%) and Tc2O5 (56%), while the main mononuclear species are TcO3 (33.9%) and TcO2 (42.8%). The difference in the relative intensities of the M2O5 (M = Tc, Re) fragments (1.7% for Re) indicates that these group 7 elements exhibit different gas-phase chemistry. The solid-state structure of Tc2O7 was investigated by density functional theory methods. The optimized structure of the Tc2O7 molecule is in good agreement with the experimental one. Simulations indicate that the more favorable geometry for the Tc2O7 molecule in the gas-phase is bent (Tc-OBri-Tc = 156.5°), while a linear geometry (Tc-OBri-Tc = 180.0°) is favored in the solid-state.},
doi = {10.1021/acs.inorgchem.6b01683},
journal = {Inorganic Chemistry},
number = 20,
volume = 55,
place = {United States},
year = {Tue Oct 04 00:00:00 EDT 2016},
month = {Tue Oct 04 00:00:00 EDT 2016}
}
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    Works referencing / citing this record:

    The Nature of the Technetium Species Formed During the Oxidation of Technetium Dioxide with Oxygen and Water
    text, January 2018

    • Childs, Bradley C.; Lawler, Keith V.; Braband, Henrik
    • Wiley-Blackwell Publishing, Inc.
    • DOI: 10.5167/uzh-153405
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