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Synthesis and structure of diarylhalotelluronium hexahalotellurates [(8-Me2 NC10 H6)2 TeX]2 TeX6 (X=Cl, Br)

  • Jens Bolsinger and Jens Beckmann EMAIL logo
Published/Copyright: September 17, 2014
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Main Group Metal Chemistry
From the journal Main Group Metal Chemistry Volume 37 Issue 5-6

Abstract

The title compounds [(8-Me2 NC10 H6)2 TeX]2 TeX6 (1, X=Cl; 2, X=Br) were obtained by the oxidation of (8-Me2 NC10 H6)2 Te with SO2 Cl2 and Br2 and the subsequent addition of TeCl4 and TeBr4, respectively, and were characterized by X-ray crystallography and multinuclear NMR spectroscopy. Due to the intramolecularly coordinating 8-dimethylaminonaphthyl substituents, 1 and 2 comprise loosely associated ion pairs of distorted trigonal bipyramidal [(8-Me2 NC10 H6)2 TeX]+ cations and octahedral TeX62- anions (X=Cl, Br).

Keywords: 125Te NMR spectroscopy; secondary bonds; structure determination; tellurium

Recently, we reported on a series of diaryltelluronium compounds [(8-Me2 NC10 H6)2 TeX]Y (X=Cl, Br, I, OH; Y=Cl, Br, I, I3, PF6, O3 SCF3) in which two intramolecularly coordinating 8-dimethylaminonaphthyl substituents gave rise to cationic structures (Beckmann et al., 2012, 2013).

The zwitterionic diaryltelluronium acetimidate, (8-Me2 NC10 H6)2 TeNC(O)CH3, obtained by an unexpected oxygen transfer from the diaryltellurium oxide, (8-Me2 NC10 H6)2 TeO, to acetonitrile belongs to the same structure type (Mallow et al., 2014). In the context of this work, we also isolated the title compounds [(8-Me2 NC10 H6)2 TeX]2 TeX6 (1, X=Cl; 2, X=Br), at first in small crops from halogenation reactions of impure (8-Me2 NC10 H6)2 Te containing small amounts of elemental tellurium. After their structural elucidation, the same products were deliberately prepared in good yields by the reaction of analytically pure (8-Me2 NC10 H6)2 Te with SO2 Cl2 and Br2, respectively, followed by the immediate addition of TeCl4 and TeBr4, respectively (Scheme 1). The last two apparently abstract chloride and bromide ions from the initially formed diarylhalotelluronium halides [(8-Me2 NC10 H6)2 TeX]X (X=Cl, Br) (Beckmann et al., 2013).

Scheme 1 Synthesis of compounds 1 and 2.
Scheme 1

Synthesis of compounds 1 and 2.

The title compounds [(8-Me2 NC10 H6)2 TeX]2 TeX6 (1, X=Cl; 2, X=Br) were obtained as yellow and brown single crystals that were substantially more stable than the initial oxidation products [(8-Me2 NC10 H6)2 TeX]X (X=Cl, Br) (Beckmann et al., 2013). The molecular structures of 1 and 2 are shown in Figures 1 and 2, respectively. Selected bond parameters were collected and are shown in the caption of the figures, and crystal and refinement data are listed in Table 1. The spatial arrangement of the Te atoms of the cations can be described in two ways. Taking into account the first coordination sphere only, it is a distorted trigonal bipyramidal setting in which C10, C20 and N2 occupy the equatorial positions, whereas N1 and Cl1 or Br1 are situated in the axial positions.

Figure 1 Molecular structure of [(8-Me2 NC10 H6)2 TeCl]2 TeCl6 (1) showing 30% probability ellipsoids and the crystallographic numbering scheme.Selected bond parameters (Å, °): Te1-Cl1 2.429(2), Te1-C20 2.118(5), Te1-C10 2.132(6), Te1-N1 2.435(5), Te1-N2 2.694(4), Cl1-Te1-C10 91.2(2), Te2-Cl2 2.527(2), Te2-Cl3 2.533(2), Te2-Cl4 2.529(2), Cl1-Te1-C20 88.41(14), C10-Te1-C20 97.2(2); ion contact: Te1···Cl2 3.291(2).
Figure 1

Molecular structure of [(8-Me2 NC10 H6)2 TeCl]2 TeCl6 (1) showing 30% probability ellipsoids and the crystallographic numbering scheme.

Selected bond parameters (Å, °): Te1-Cl1 2.429(2), Te1-C20 2.118(5), Te1-C10 2.132(6), Te1-N1 2.435(5), Te1-N2 2.694(4), Cl1-Te1-C10 91.2(2), Te2-Cl2 2.527(2), Te2-Cl3 2.533(2), Te2-Cl4 2.529(2), Cl1-Te1-C20 88.41(14), C10-Te1-C20 97.2(2); ion contact: Te1···Cl2 3.291(2).

Figure 2 Molecular structure of [(8-Me2 NC10 H6)2 TeBr]2 TeBr6 (2) showing 30% probability ellipsoids and the crystallographic numbering scheme.Selected bond parameters (Å, °): Te1-Br1 2.594(2), Te1-C10 2.14(1), Te1-C20 2.138(9), Te1-N1 2.381(7), Te1-N2 2.81(1), Te2-Br2 2.694(1), Te2-Br3 2.687(1), Te2-Br4 2.690(2), Br1-Te1-C10 92.9(3), Br1-Te1-C20 92.5(2), C10-Te1-C20 94.3(3); ion contact: Te1···Br2 3.570(2).
Figure 2

Molecular structure of [(8-Me2 NC10 H6)2 TeBr]2 TeBr6 (2) showing 30% probability ellipsoids and the crystallographic numbering scheme.

Selected bond parameters (Å, °): Te1-Br1 2.594(2), Te1-C10 2.14(1), Te1-C20 2.138(9), Te1-N1 2.381(7), Te1-N2 2.81(1), Te2-Br2 2.694(1), Te2-Br3 2.687(1), Te2-Br4 2.690(2), Br1-Te1-C10 92.9(3), Br1-Te1-C20 92.5(2), C10-Te1-C20 94.3(3); ion contact: Te1···Br2 3.570(2).

Table 1

Crystal data and structure refinement of compounds 1 and 2.

1·2 MeCN2·2 CHCl3
FormulaC52 H54 Cl8 N6 Te3C50 H50 Br8 Cl6 N4 Te3
Formula weight, g/mol1429.411941.72
Crystal systemTriclinicTriclinic
Crystal size, mm0.15×0.10×0.040.15×0.10×0.05
Space groupP-1P-1
a, Å9.177(4)8.299(5)
b, Å11.095(4)11.832(5)
c, Å14.215(4)16.083(5)
α, °86.75(4)82.640(5)
β, °80.96(4)88.065(5)
γ, °81.26(4)81.127(5)
V, Å31411.9(12)1547.3(12)
Z11
ρcalcd, Mg/m31.6812.084
T, K150150
μ (Mo Kα), mm-11.9596.866
F(000)700916
θ range, °2.50–25.252.30–26.00
Index ranges-11≤h≤11-8≤h≤10
-13≤k≤13-14≤k≤14
-17≤l≤16-19≤l≤19
No. of reflections collected10,94013,418
Completeness to θmax99.1%99.6%
No. of independent reflections50476046
No. of observed reflections with [I>2σ(I)]24313496
No. of refined parameters313322
GooF (F2)0.8540.868
R1 (F) [I>2σ(I)]0.03500.0526
wR2 (F2) (all data)0.05510.1101
(Δ/σ)max<0.01<0.01
Largest difference peak/hole, e/Å-30.497/-0.5251.069/-1.106
CCDC999867999868

GooF, goodness of fit.

The Te1-Cl1 bond length of 1 [2.429(2) Å] and the Te1-Br1 bond length of 2 [2.594(2) Å] are slightly shorter than those of Ph2 TeCl2 [2.506(2) Å] (Alcock and Harrison, 1982) and Ph2 TeBr2 [2.6818(6) Å] (Beckmann et al., 2004).

The axial Te1-N1 bond lengths of 1 [2.435(5) Å] and 2 [2.381(7) Å] are shorter than the equatorial Te1-N2 bond lengths of 1 [2.694(4) Å] and 2 [2.81(1) Å], thus contradicting Bent’s (1961) rule. Overall, these parameters are very similar to those of [(8-Me2 NC10 H6)2 TeX]X (X=Cl, Br) (Beckmann et al., 2013). Besides the first coordination sphere, there is a secondary contact arising from ion pairing. The related Te1···Cl2 [3.291(2) Å] and Te1···Br2 [3.570(2) Å] bond distances of 1 and 2 are slightly longer than those of [(8-Me2 NC10 H6)2 TeX]X [X=Cl: 3.173(1) Å; X=Br: 3.411(4) Å] (Beckmann et al., 2013). Thus, considering also the second coordination sphere, the spatial arrangement of the Te atoms of the cations can be regarded as strongly distorted octahedral. In the counterions, TeX62- of 1 (X=Cl) and 2 (X=Br), the Te atoms adopt only slightly distorted octahedral arrangements. The average Te2-Cl bond lengths of 1 [2.530(2) Å] and the average Te-Br bond lengths of 2 [2.690(2) Å] closely resemble those of known hexahalotellurate ions, [Me2 SO)2 H]2[TeCl6] [2.537(1) Å] (Pietikäinen et al., 2002), [Ph3 Te]2[TeCl6] [2.545(1) Å] (Närhi et al., 2004) and [PhMe2 Te]2[TeBr6] [2.71(2) Å] (Santos dos Santos et al., 2007).

Like [(8-Me2 NC10 H6)2 TeX]X (X=Cl, Br) (Beckmann et al., 2013), [(8-Me2 NC10 H6)2 TeX]2 TeX6 (1, X=Cl; 2, X=Br) are best soluble in polar solvents such as acetonitrile, where they undergo electrolytic dissociation. The 125Te NMR spectra (CDCN) of 1 and 2 show two signals at δ=1201.0 and 1471.6 ppm and δ=1190.9 and 1365.6 ppm in integral ratios of 2:1, which are unambiguously assigned to the [(8-Me2 NC10 H6)2 TeX]+ cations and TeX62- anions, respectively (X=Cl, Br). The 1H NMR spectra (CDCN) of 1 and 2 show four signals in the aliphatic range, demonstrating that the two 8-dimethylaminonaphthyl groups are magnetically inequivalent, which is consistent with the idea that the spatial arrangement of the cations in the solid state is retained in solution.

Experimental

General

Bis(8-dimethylaminonaphthyl)telluride was prepared according to literature procedure (Beckmann et al., 2012). The 1H, 13C and 125Te NMR spectra were recorded using the Jeol GX 270 and Varian 300 Unity Plus spectrometers and were referenced to SiMe4 (1H, 13C) and Me2 Te (125Te). Microanalyses were obtained from a Vario EL elemental analyzer.

Synthesis of [(8-Me2 NC10 H6)2 TeCl]2 TeCl6 (1)

To a solution of bis(8-dimethylaminonaphtyl)telluride (520 mg, 1.11 mmol) in dry tetrahydrofuran (THF) (20 mL), sulfuryl chloride (150 mg, 1.11 mmol) was added and stirred for 15 min. Then a solution of tellurium tetrachloride (299 mg, 1.11 mmol) in THF (10 mL) was added. Directly after the addition, a yellow powder precipitated, which was collected by filtration. The crude product was dissolved in acetonitrile (40 mL), and slow evaporation of the solvent yielded yellow crystals of 1 [450 mg, 0.33 mmol, 55%; Mp. 224–229°C (dec.)].

1H NMR (CDCN): δ=8.80 (d, 1H); 8.46 (d, 1H); 8.16 (m, 2H); 8.07 (t, 1H); 7.97 (m, 2H), 7.78 (m, 3H), 7.28 (t, 1H;), 7.01 (d, 1H) (C10 H6), 3.24 (s, 3H); 3.08 (s, 3H); 3.04 (s, 3H), 2.38 (s, 3H). 125Te NMR (CDCN): δ=1201.0 (2Te), 1471.6 (1Te). Anal. Calcd. for C48 H48 N4 Cl8 Te3 (1347.35): C 42.79, H 3.59; N 4.16. Found: C 43.06, H 3.45; N 3.98.

Synthesis of [(8-Me2 NC10 H6)2 TeBr]2 TeBr6 (2)

To a solution of bis(8-dimethylaminonaphtyl)telluride (468 mg, 1.00 mmol) in dry THF (10 mL), dibromine (160 mg, 1.00 mmol) was added and stirred for 15 min. Then a solution of tellurium tetrabromide (447 mg, 1.00 mmol) in THF (10 mL) was added. Directly after the addition, an orange brown powder precipitated, which was collected by filtration. The crude product was dissolved in hot CHCl3 (40 mL). Slow evaporation of the solvent yielded brown crystals of 2 [610 mg, 0.36 mmol, 67%; Mp. 200–210°C (dec.)].

1H NMR (CDCN, -35°C): δ=8.88 (d, 1H); 8.48 (d, 1H); 8.18 (m, 2H); 8.04 (t, 1H); 7.97 (m, 2H), 7.86–7.72 (m, 3H), 7.26 (t, 1H;), 7.02 (d, 1H) (C10 H6), 3.20 (s, 3H); 3.13 (s, 3H); 3.03 (s, 3H), 2.40 (s, 3H). 125Te NMR (CDCN): δ=1190.9 (2Te), 1365.6 (1Te). Anal. Calcd. for C48 H48 N4 Br8 Te3 (1702.95): C 33.85, H 2.84; N 3.29 Found: C 33.65, H 2.55; N 3.13.

X-ray crystallography

The intensity data of 1 and 2 were collected on a STOE IPDS 2T area detector with graphite-monochromated Mo-Kα (0.7107 Å) radiation. The structures were solved by direct methods and difference Fourier synthesis using SHELXS-97 implemented in the program WinGX 2002 (Farrugia, 1999). Full-matrix least-squares refinements on F2, using all data. All non-hydrogen atoms were refined using anisotropic displacement parameters. Hydrogen atoms attached to carbon atoms were included in geometrically calculated positions using a riding model and were refined isotropically. The four hydrogen atoms attached to the oxygen atoms of 1 were located during the last refinement cycle and refined isotropically. Crystal and refinement data are collected in Table 1. Figures were created using the DIAMOND software (Brandenburg and Putz, 2006). Crystallographic data (excluding structure factors) for the structural analyses have been deposited with the Cambridge Crystallographic Data Centre. Copies of this information may be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: +44-1223-336033; e-mail: or http://www.ccdc.cam.ac.uk).

Corresponding author: Jens Beckmann, Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstraße 36a, D-14195 Berlin, Germany, e-mail: ; and Institut für Anorganische Chemie, Universität Bremen, Leobener Straße, D-28359 Bremen, Germany

Acknowledgments

The Deutsche Forschungsgemeinschaft (DFG) is gratefully acknowledged for financial support.

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Received: 2014-7-4
Accepted: 2014-8-14
Published Online: 2014-9-17
Published in Print: 2014-12-1

©2014 by De Gruyter

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https://doi.org/10.1515/mgmc-2014-0022
Keywords for this article
125Te NMR spectroscopy; secondary bonds; structure determination; tellurium
Creative Commons
BY-NC-ND 3.0

Articles in the same Issue

  1. Frontmatter
  2. Research Articles
  3. Synthesis and structure of an acyclic dialkylstannylene
  4. Two in one: the bismuth bromido clusters in [Bi6Cp*6Br9][Bi7Br24]
  5. 2D Hydrogen-bonded polymer assembled by zinc(II) tetraaza macrocyclic complex and 1,2-cyclopentanedicarboxylic acid
  6. An efficient synthesis of N-substituted pyrroles catalyzed by MgI2 etherate
  7. Synthesis and characterization of N2S2-tin macrocyclic complexes of Co(II), Ni(II), Cu(II) and Zn(II)
  8. Synthesis, characterization and in vitro cytotoxic activity of bis(triorganotin) 2,6-pyridinedicarboxylates
  9. Short Communications
  10. Reactivity of a spirobis(pentagerma[1.1.1]propellane)
  11. A monoclinic polymorph of 2,6-Mes2 C6 H3 SiF3
  12. Synthesis and structure of bis(m-terphenyl)zinc (2,6-Mes2 C6 H3)2 Zn
  13. Synthesis and structure of diarylhalotelluronium hexahalotellurates [(8-Me2 NC10 H6)2 TeX]2 TeX6 (X=Cl, Br)
  14. Synthesis and structure of three molecular arylindium phosphinates
  15. Molecular structure of Te2 Mg2(μ3-Cl2)(μ2-Cl4)Cl6(THF)4·CH2 Cl2
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