The structure of the tetrachlorohydroxotellurate(IV) anion in KTeCl4(OH)•0.5H2O and KTeCl4(OH)

Milne, J. B.; Gabe, E. J.; Bensimon, Corinne

doi:10.1139/v91-098

Cited by 7 publications

(6 citation statements)

References 13 publications

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“…The anhydrous version of the title compound, K[TeCl 4 (OH)], was suggested polymeric with chlorine bridging [29]. In such a case, the C Q ( 35 Cl) quadrupole coupling constant is expected to be significantly reduced to as low as 10-15 MHz, as was reported for a number of covalent transition-metal chlorides containing Cl bridging [21][22][23].…”

Section: Resultsmentioning

confidence: 91%

“…The crystal structure was solved as monoclinic, space group P2 1 /c [29]. The unit cell contains two types of isolated and somewhat distorted square pyramidal TeCl 4 (OH) -ions (OH axial), one of which is disordered over two sites.…”

Section: Resultsmentioning

confidence: 99%

“…Triphenyltellurium chloride, Ph 3 TeCl, was purchased from Organometallics Inc. (USA) and was used as received. The synthesis of K[TeCl 4 (OH)]⋅0.5H 2 O is described in [29]. 35 [14,15] was used to acquire wideline 35 Cl NMR spectra in a frequency-offset manner.…”

Section: Methodsmentioning

confidence: 99%

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

2016

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We report solid-state 35 Cl NMR spectra in three hexachlorides, (NH 4 ) 2 SeCl 6 , (NH 4 ) 2 TeCl 6 and Rb 2 TeCl 6 .The C Q ( 35 Cl) 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 ( 35 Cl) quadrupole coupling constants ever measured in polycrystalline powdered solids directly via 35 Cl NMR spectroscopy. The 35 Cl EFG tensors are axial in all three cases reflecting the C 4v point group symmetry of the chlorine sites. 35 Cl 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. 35 Cl NMR results agree with the earlier reported 35 Cl NQR values and with the complementary plane-wave DFT calculations. The origin of the very large C Q ( 35 Cl) 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 ( 35 Cl) values as illustrated with triphenyltellurium chloride Ph 3 TeCl. The high sensitivity of 35 Cl NMR to the chlorine coordination environment is demonstrated using tetrachlorohydroxotellurate hydrate K[TeCl 4 (OH)]⋅0.5H 2 O as an example. 125 Te MAS NMR experiments were performed for tellurium compounds to support 35 Cl NMR findings.

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Section: Resultsmentioning

confidence: 91%

Section: Resultsmentioning

confidence: 99%

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

2016

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“…A reconsideration of this problem is occasioned by the successful treatment of equilibria involving Se(1V) species in hydrohalic acids (2,3). This represents an extension of previous work concerning the complexes of tellurium (4).…”

Section: Introductionmentioning

confidence: 90%

Hexachlorotellurate(IV) hydrolysis equilibria in hydrochloric acid. Measurement by Raman and ¹²⁵Te NMR spectroscopy and a reconsideration of earlier spectrophotometric results

Milne¹

1991

Can. J. Chem.

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J. B. MILNE. Can. J. Cl~em. 69, 987 (1991). Solutions of Te02 (0.001 M) in HCI over a range of concentrations are shown to contain TeC12(0H)2 in addition to and TeC14(OH)-. The hydrolysis constants for ~e C 1~~-and TeC14(0H)-have been determined from a reconsideration of earlier UV-visible spectrophotometric results (1) The hydrolysis constants have also been determined by quantitative Raman spectroscopy (K1 = 2.21 (* 0.16) x lo4 M3; K2 = 442 ? 57 M3). The agreement between K2 determined by the two methods is good but K, from spectrophotometry is much larger than that from Raman studies. This disagreement is attributed to ion-pairing which will be significant at the concentration at which the Raman measurements were made (c(Te02) = 0.50 M). The hydrolysis constant for ~e~1~~-was also determined from the I z 5~e NMR spectra of Te02/HC1 solutions, which consisted of one signal, indicating rapid Te exchange between all species. The hydrolysis constant, determined in this way (KI = 1.92 (* 0.07) x lo4 M3) was also low compared to that determined from spectrophotometry .Key words: solution, equilibria, tellurium, hydrochloric acid, Raman spectroscopy, 1 2 5~e NMR spectroscopy, UV-visible spectrophotometry . Les constantes d'hydrolyse ont Ct C aussi determinkes en faisant appel a la spectroscopie Raman quantitative (K, = 2,21 ( 5 0,16) X lo4 M3; K2 = 442 5 57 M3). L'accord entre le K2 evaluC par les deux mCthodes est bon, mais le Kl Cvalut par le spectrophotomCtrie est plus grand que celvi CvaluC par la spectroscopie Raman. Ce dCsaccord est attribuC a la formation de paires d'ions qui sont importantes aux concentrations utilisCes pour mesurer les spectres Raman (c(Te02) = 0,5 M). La constante d'hydrolyse de ~e~1 6 ' -a aussi Ct C CvaluCe en faisant appel h la spectroscopie RMN du sur des solutions de Te02 dans le HC1. Les spectres montrent une seule bande qui indique 1'Cchange rapide de Te. La constante d'hydrolyse, CvaluCe par la spectroscopie RMN (KI = 1,92 (? 0,07) X lo4 M~) est aussi basse comparCe a celle CvaluCe par la spectrophotomCtrie.

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“…Dark red crystals of the composition [H30][TeBr5] * 3 C4H802 (1) were isolated from a saturated solution of TeBr, in 1,Cdioxane containing a small amount of water. In this compound (space group P2,/m, a = 8.922 (4) A, b = 13.204 (7) A, c = 9.853 (5) A, p = 91.82(4)" at l50K) a square pyramidal [TeBr,]-anion has been isolated for the first time. The coordination sphere of the anion is completed to a distorted octahedron by weak interaction with a dioxane molecule of the cationic system.…”

Section: New Oxonium Bromochalcogenates(1v) -Synthesis Structure Anmentioning

confidence: 98%

Neue Oxonium‐Bromochalkogenate(IV) — Darstellung, Struktur und Eigenschaften von [H₃O][TeBr₅] · 3C₄H₈O₂ und [H₃O]₂[SeBr₆]

Reich

Hasche

Büscher

et al. 1996

Zeitschrift anorg allge chemie

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Tiefrote Kristalle der Zusammensetzung [H3O][TeBr5] · 3 C4H8O2 (1) wurden aus einer gesättigten Lösung von TeBr4 in wasserhaltigem 1,4‐Dioxan dargestellt. In der Verbindung (Raumgruppe P21/m, a = 8.922(4) Å, b = 13.204(7) Å, c = 9.853(5) Å, β = 91.82(4)° bei 150 K) konnte erstmals ein quadratisch‐pyramidales [TeBr5]− ‐Anion isoliert werden. Dessen Koordinationspolyeder wird durch eine schwache Wechselwirkung mit einem 1,4‐Dioxan‐Molekül zu einem verzerrten Oktaeder vervollständigt. Die [H3O]+‐Kationen sind durch 1,4‐Dioxan‐Moleküle zu Ketten verknüpft. Die Säure ist bei Raumtemperatur nur in ihrer Mutterlauge stabil. [H3O]2[SeBr6] (2) (Raumgruppe Fm3m, a = 10.421(1) Å bei 170 K) ist eine hochsymmetrisch kristallisierende Bromoselen(IV)‐säure, mit der es gelang, ein nur sehr schwach durch Br‐Atome des Anions koordiniertes [H3O]+‐Ion zu isolieren. Die anionische Einheit besteht aus freien, unverzerrt oktaedrischen [SeBr6]2−‐Ionen. Die Kristallstruktur ist isotyp zu K2[PtCl6]. Die Verbindung zeigt eine für Halogenochalkogen(IV)‐säuren bemerkenswerte thermische Stabilität. Beide Oxoniumsalze wurden durch vollständige Röntgenstrukturanalysen charakterisiert. Über schwingungsspektroskopische Untersuchungen an 2 wird berichtet.

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The structure of the tetrachlorohydroxotellurate(IV) anion in KTeCl₄(OH)•0.5H₂O and KTeCl₄(OH)

Cited by 7 publications

References 13 publications

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

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

Hexachlorotellurate(IV) hydrolysis equilibria in hydrochloric acid. Measurement by Raman and ¹²⁵Te NMR spectroscopy and a reconsideration of earlier spectrophotometric results

Neue Oxonium‐Bromochalkogenate(IV) — Darstellung, Struktur und Eigenschaften von [H₃O][TeBr₅] · 3C₄H₈O₂ und [H₃O]₂[SeBr₆]

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The structure of the tetrachlorohydroxotellurate(IV) anion in KTeCl4(OH)•0.5H2O and KTeCl4(OH)

Cited by 7 publications

References 13 publications

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

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

Hexachlorotellurate(IV) hydrolysis equilibria in hydrochloric acid. Measurement by Raman and 125Te NMR spectroscopy and a reconsideration of earlier spectrophotometric results

Neue Oxonium‐Bromochalkogenate(IV) — Darstellung, Struktur und Eigenschaften von [H3O][TeBr5] · 3C4H8O2 und [H3O]2[SeBr6]

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The structure of the tetrachlorohydroxotellurate(IV) anion in KTeCl₄(OH)•0.5H₂O and KTeCl₄(OH)

Hexachlorotellurate(IV) hydrolysis equilibria in hydrochloric acid. Measurement by Raman and ¹²⁵Te NMR spectroscopy and a reconsideration of earlier spectrophotometric results

Neue Oxonium‐Bromochalkogenate(IV) — Darstellung, Struktur und Eigenschaften von [H₃O][TeBr₅] · 3C₄H₈O₂ und [H₃O]₂[SeBr₆]