Header

UZH-Logo

Maintenance Infos

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


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 (2016). Ditechnetium heptoxide revisited: solid-state, gas-phase, and theoretical studies. Inorganic Chemistry, 55(20):10445-10452.

Abstract

Ditechnetium heptoxide was synthesized from the oxidation of TcO2 with O-2 at 450 degrees 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) angstrom, b = 5.562(2) angstrom, c = 13.707(5) angstrom, and V = 557.5(3) angstrom(3)]. The Tc2O7 molecule can be described as corner-sharing TcO4 tetrahedron [Tc---Tc = 3.698(1) angstrom and Tc-O-Bri-Tc = 180.0 degrees]. 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-O-Bri-Tc = 156.5 degrees), while a linear geometry (Tc-O-Bri-Tc = 180.0 degrees) is favored in the solid-state.

Abstract

Ditechnetium heptoxide was synthesized from the oxidation of TcO2 with O-2 at 450 degrees 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) angstrom, b = 5.562(2) angstrom, c = 13.707(5) angstrom, and V = 557.5(3) angstrom(3)]. The Tc2O7 molecule can be described as corner-sharing TcO4 tetrahedron [Tc---Tc = 3.698(1) angstrom and Tc-O-Bri-Tc = 180.0 degrees]. 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-O-Bri-Tc = 156.5 degrees), while a linear geometry (Tc-O-Bri-Tc = 180.0 degrees) is favored in the solid-state.

Statistics

Citations

1 citation in Web of Science®
1 citation in Scopus®
Google Scholar™

Altmetrics

Downloads

0 downloads since deposited on 06 Feb 2017
0 downloads since 12 months

Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:17 October 2016
Deposited On:06 Feb 2017 15:28
Last Modified:12 Feb 2017 06:57
Publisher:American Chemical Society (ACS)
ISSN:0020-1669
Funders:Integrated University Program Graduate Fellowship, National Nuclear Security Administration under the Stewardship Science Academic Alliances program through DOE
Publisher DOI:https://doi.org/10.1021/acs.inorgchem.6b01683
PubMed ID:27700061

Download

Preview Icon on Download
Content: Published Version
Filetype: PDF - Registered users only
Size: 3MB
View at publisher

TrendTerms

TrendTerms displays relevant terms of the abstract of this publication and related documents on a map. The terms and their relations were extracted from ZORA using word statistics. Their timelines are taken from ZORA as well. The bubble size of a term is proportional to the number of documents where the term occurs. Red, orange, yellow and green colors are used for terms that occur in the current document; red indicates high interlinkedness of a term with other terms, orange, yellow and green decreasing interlinkedness. Blue is used for terms that have a relation with the terms in this document, but occur in other documents.
You can navigate and zoom the map. Mouse-hovering a term displays its timeline, clicking it yields the associated documents.

Author Collaborations