High-field solid-state ³⁵Cl NMR in selenium(IV) and tellurium(IV) hexachlorides

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DOIResolve DOI: http://doi.org/10.1134/S0022476616020104
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TypeArticle
Journal titleJournal of Structural Chemistry
ISSN0022-4766
1573-8779
Volume57
Issue2
Pages308318
Subject³⁵Cl NMR; ³⁵Cl NQR; Selenium; Tellurium; Hexachloride; DFT calculations; CASTEP NMR
AbstractWe report solid-state ³⁵Cl NMR spectra in three hexachlorides, (NH₄)₂SeCl₆, (NH₄)₂TeCl₆ and Rb₂TeCl₆. The C Q (³⁵Cl) quadrupole coupling constants in the three compounds were found to be 41.4±0.1 MHz, 30.3±0.1 MHz and 30.3±0.1 MHz, respectively, some of the largest C Q (³⁵Cl) quadrupole coupling constants ever measured in polycrystalline powdered solids directly via ³⁵Cl NMR spectroscopy. The ³⁵Cl EFG tensors are axial in all three cases reflecting the C ₄ᵥ point group symmetry of the chlorine sites. ³⁵Cl NMR experiments in these compounds were only made possible by employing the WURST-QCPMG pulse sequence in the ultrahigh magnetic field of 21.1 T. ³⁵Cl NMR results agree with the earlier reported ³⁵Cl NQR values and with the complementary plane-wave DFT calculations. The origin of the very large C Q (³⁵Cl) quadrupole coupling constants in these and other main-group chlorides lies in the covalent-type chlorine bonding. The ionic bonding in the ionic chlorides results in significantly reduced C Q (³⁵Cl) values as illustrated with triphenyltellurium chloride Ph₃TeCl. The high sensitivity of ³⁵Cl NMR to the chlorine coordination environment is demonstrated using tetrachlorohydroxotellurate hydrate K[TeCl₄(OH)]∙0.5H₂O as an example. ¹²⁵Te MAS NMR experiments were performed for tellurium compounds to support ³⁵Cl NMR findings.
Publication date
PublisherSpringer International Publishing
LanguageEnglish
AffiliationSecurity and Disruptive Technologies; National Research Council Canada
Peer reviewedYes
Identifier368
NPARC number23000403
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Record identifierced94e84-cc64-46a6-a416-dacc2056e741
Record created2016-07-13
Record modified2016-07-13
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