Reactions with oleum under harsh conditions : characterization of the unique [M(S2O7)3]2- ions (M=Si, Ge, Sn) in A2[M(S2O7)3] (A=NH4, Ag) Logemann, Christian, Gunzelmann, Daniel, Kluner, Thorsten, Senker, Jurgen and Wickleder, Mathias S. 2012, Reactions with oleum under harsh conditions : characterization of the unique [M(S2O7)3]2- ions (M=Si, Ge, Sn) in A2[M(S2O7)3] (A=NH4, Ag), Chemistry : a European journal, vol. 18, no. 48, pp. 15495-15503, doi: 10.1002/chem.201202344. Attached Files Name Description MIMEType Size Downloads Title Reactions with oleum under harsh conditions : characterization of the unique [M(S2O7)3]2- ions (M=Si, Ge, Sn) in A2[M(S2O7)3] (A=NH4, Ag) Author(s) Logemann, Christian Gunzelmann, Daniel Kluner, Thorsten Senker, Jurgen Wickleder, Mathias S. Journal name Chemistry : a European journal Volume number 18 Issue number 48 Start page 15495 End page 15503 Total pages 9 Publisher Wiley Place of publication London, Eng. Publication date 2012-11-26 ISSN 1521-3765 Keyword(s) density functional calculations disulfates NMR spectroscopy thermal decomposition vibrational spectroscopy Summary The reactions of group 14 tetrachlorides MCl4 (M=Si, Ge, Sn) with oleum (65 % SO3) at elevated temperatures lead to the unique complex ions [M(S2O7)3]2−, which show the central M atoms in coordination with three chelating S2O72− groups. The mean distances M[BOND]O within the anions increase from 175.6(2)–177.5(2) pm (M=Si) to 186.4(4)–187.7(4) pm (M=Ge) to 201.9(2)–203.5(2) pm (M=Sn). These distances are reproduced well by DFT calculations. The same calculations show an increasing positive charge for the central M atom in the row Si, Ge, Sn, which can be interpreted as the decreasing covalency of the M[BOND]O bonds. For the silicon compound (NH4)2[Si(S2O7)3], 29Si solid-state NMR measurements have been performed, with the results showing a signal at −215.5 ppm for (NH4)2[Si(S2O7)3], which is in very good agreement with theoretical estimations. In addition, the vibrational modes within the [MO6] skeleton have been monitored by Raman spectroscopy for selected examples, and are well reproduced by theory. The charge balance for the [M(S2O7)3]2− ions is achieved by monovalent A+ counter ions (A=NH4, Ag), which are implemented in the syntheses in the form of their sulfates. The sizes of the A+ ions, that is, their coordination requirements, cause the crystallographic differences in the crystal structures, although the complex [M(S2O7)3]2− ions remain essentially unaffected with the different A+ ions. Furthermore, the nature of the A+ ions influences the thermal behavior of the compounds, which has been monitored for selected examples by thermogravimetric differential thermal analysis (DTA/TG) and XRD measurements. Language eng DOI 10.1002/chem.201202344 Field of Research 039999 Chemical Sciences not elsewhere classified Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences HERDC Research category C1.1 Refereed article in a scholarly journal Copyright notice ©2012, Wiley Free to Read? Yes Persistent URL http://hdl.handle.net/10536/DRO/DU:30064409 Document type: Journal Article Collections: Institute for Frontier Materials Open Access Collection GTP Research Related Links Link Description Link to full-text (open access)   Connect to published version (restricted access) Go to link with your DU access privileges     Unless expressly stated otherwise, the copyright for items in DRO is owned by the author, with all rights reserved. Every reasonable effort has been made to ensure that permission has been obtained for items included in DRO. If you believe that your rights have been infringed by this repository, please contact drosupport@deakin.edu.au. Versions Version Filter Type Fri, 13 Jun 2014, 12:12:18 EST Mon, 16 Jun 2014, 08:48:19 EST Fri, 20 Jun 2014, 14:50:59 EST Thu, 11 Dec 2014, 20:37:15 EST Wed, 23 Dec 2020, 04:39:08 EST Filtered Full Citation counts:   Cited 21 times in TR Web of Science Cited 21 times in Scopus Search Google Scholar Access Statistics: 219 Abstract Views, 1 File Downloads  -  Detailed Statistics Created: Fri, 13 Jun 2014, 12:12:18 EST

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