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

Here, ditechnetium heptoxide was synthesized from the oxidation of TcO 2 with O 2 at 450 °C and characterized by single crystal X-ray diffraction (SCXRD), electron impact mass spectrometry (EI-MS) and theoretical methods. Refinement of the structure at 100 K indicates that Tc 2O 7 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, V = 557.5(3) Å 3). The Tc 2O 7 molecule can be described as corner-sharing TcO4 tetrahedra (Tc---Tc = 3.698(1) Å and Tc-O Bri-Tc = 180.0°). The EI-MS spectrum of Tc 2O 7 consists of both mononuclear and dinuclear species. The main dinuclear species in the gas-phase are Tc 2O 7 (100%) and Tc 2O 5 (56%), while the main mononuclear species are TcO 3 (33.9%) and TcO 2 (42.8%). The difference in the relative intensities of the M 2O 5 (M = Tc, Re) fragments (1.7% for Re) indicate that these Group 7 elements exhibit different gas phase chemistry. The solid-state structure of Tc 2O 7 was investigated by density functional theory (DFT) methods. The optimized structure of the Tc 2O 7 molecule is in good agreement with the experimental one.more » Simulations indicate that the more favorable geometry for the Tc 2O 7 molecule in the gas-phase is bent (Tc-O Bri-Tc = 156.5°), while linear (Tc-O Bri-Tc = 180.0°) is favored in the solid state.« less
Authors:
 [1] ;  [2] ;  [1] ;  [1] ;  [2] ;  [2] ;  [1] ;  [1] ;  [2] ;  [3] ;  [1]
  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:
Grant/Contract Number:
AC02-06CH11357; NA0003180
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)
Research Org:
Argonne National Lab. (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)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1339618
Alternate Identifier(s):
OSTI ID: 1405177

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., Web. doi:10.1021/acs.inorgchem.6b01683.
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. doi:10.1021/acs.inorgchem.6b01683.
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. 2016. "Ditechnetium heptoxide revisited: Solid-state, gas-phase, and theoretical studies". United States. doi:10.1021/acs.inorgchem.6b01683. https://www.osti.gov/servlets/purl/1339618.
@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 = {Here, ditechnetium heptoxide was synthesized from the oxidation of TcO2 with O2 at 450 °C and characterized by single crystal X-ray diffraction (SCXRD), 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, V = 557.5(3) Å3). The Tc2O7 molecule can be described as corner-sharing TcO4 tetrahedra (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) indicate that these Group 7 elements exhibit different gas phase chemistry. The solid-state structure of Tc2O7 was investigated by density functional theory (DFT) 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 linear (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 = {2016},
month = {10}
}