Tris[pentafluorotellurato(VI)]boron(III)

Sawyer, J. F.; Schrobilgen, G. J.

doi:10.1107/s0567740882006384

Cited by 13 publications

(12 citation statements)

References 7 publications

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“…The Sb−O distances Sb(2)−O(1) (1.947(5) [1.952(5)] Å) and Sb(3)−O(2)/O(3) (1.938(4)/1.938(4) [1.949(5)/1.950(5)] Å) are comparable to the average librationally corrected Sb V −O distances observed in N(CH 3 ) 4 + Sb(OTeF 5 ) 6 - and N(CH 2 CH 3 ) 4 + Sb(OTeF 5 ) 6 - (1.96 and 1.91 Å, respectively), Cs 3 Sb 3 F 12 O 3 (1.92 Å), and Rb 2 (Sb 2 F 10 O) (1.91 Å), where the Sb atoms are also octahedrally coordinated to bridging oxygen atoms. The Te−O (1.835(4) [1.831(5)] Å) and the average Te−F (1.825(5) [1.826(5)] Å) bond distances (Table ), are comparable to those found in many other OTeF 5 compounds. ,, The Sb−O−Te angles reported here (Sb(2)−O(1)−Te(1) = 139.1(3)° [139.8(3)°]; Sb(3)−O(2)/O(3)−Te(2) = 142.1(5)/142.1(5)° [142.3(6)/141.7(6)°]), differ from those reported previously for N(CH 3 ) 4 + Sb(OTeF 5 ) 6 - (148.4(8)−153.4(8)°) and N(CH 2 CH 3 ) 4 + Sb(OTeF 5 ) 6 - (160.7(9)−167(1)°), but are identical to those reported for N(CH 3 ) 4 + As(OTeF 5 ) 6 - (139.9(6)−141(2)°, R 3̄ space group) …”

Section: Resultssupporting

confidence: 75%

Tetrachloro- and Tetrabromostibonium(V) Cations: Raman and ¹⁹F, ¹²¹Sb, and ¹²³Sb NMR Spectroscopic Characterization and X-ray Crystal Structures of SbCl₄⁺Sb(OTeF₅)₆^- and SbBr₄⁺Sb(OTeF₅)₆^-

et al. 1996

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The stable salts, SbCl(4)(+)Sb(OTeF(5))(6)(-) and SbBr(4)(+)Sb(OTeF(5))(6)(-), have been prepared by oxidation of Sb(OTeF(5))(3) with Cl(2) and Br(2), respectively. The SbBr(4)(+) cation is reported for the first time and is only the second example of a tetrahalostibonium(V) cation. The SbCl(4)(+) cation had been previously characterized as the Sb(2)F(11)(-), Sb(2)Cl(2)F(9)(-), and Sb(2)Cl(0.5)F(10.5)(-) salts. Both Sb(OTeF(5))(6)(-) salts have been characterized in the solid state by low-temperature Raman spectroscopy and X-ray crystallography. Owing to the weakly coordinating nature of the Sb(OTeF(5))(6)(-) anion, both salts are readily soluble in SO(2)ClF and have been characterized in solution by (121)Sb, (123)Sb, and (19)F NMR spectroscopy. The tetrahedral environments around the Sb atoms of the cations result in low electric field gradients at the quadrupolar (121)Sb and (123)Sb nuclei and correspondingly long relaxation times, allowing the first solution NMR characterization of a tetrahalocation of the heavy pnicogens. The following crystal structures are reported: SbCl(4)(+)Sb(OTeF(5))(6)(-), trigonal system, space group P&thremacr;, a = 10.022(1) Å, c = 18.995(4) Å, V = 1652.3(6) Å(3), D(calc) = 3.652 g cm(-)(3), Z = 2, R(1) = 0.0461; SbBr(4)(+)Sb(OTeF(5))(6)(-), trigonal system, space group P&thremacr;, a = 10.206(1) Å, c = 19.297(3) Å, V = 1740.9(5) Å(3), D(calc) = 3.806 g cm(-)(3), Z = 2, R(1) = 0.0425. The crystal structures of both Sb(OTeF(5))(6)(-) salts are similar and reveal considerably weaker interactions between anion and cation than in previously known SbCl(4)(+) salts. Both cations are undistorted tetrahedra with bond lengths of 2.221(3) Å for SbCl(4)(+) and 2.385(2) Å for SbBr(4)(+). The Raman spectra are consistent with undistorted SbX(4)(+) tetrahedra and have been assigned under T(d)() point symmetry. Trends within groups 15 and 17 are noted among the general valence force constants of the PI(4)(+), AsF(4)(+), AsBr(4)(+), AsI(4)(+), SbCl(4)(+) and SbBr(4)(+) cations, which have been calculated for the first time, and the previously determined force constants for NF(4)(+), NCl(4)(+), PF(4)(+), PCl(4)(+), PBr(4)(+), and AsCl(4)(+), which have been recalculated for the P and As cations in the present study. The SbCl(4)(+) salt is stable in SO(2)ClF solution, whereas the SbBr(4)(+) salt decomposes slowly in SO(2)ClF at room temperature and rapidly in the presence of Br(-) ion and in CH(3)CN solution at low temperatures. The major products of the decompositions are SbBr(2)(+)Sb(OTeF(5))(6)(-), as an adduct with CH(3)CN in CH(3)CN solvent, and Br(2).

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Section: Resultssupporting

confidence: 75%

Tetrachloro- and Tetrabromostibonium(V) Cations: Raman and ¹⁹F, ¹²¹Sb, and ¹²³Sb NMR Spectroscopic Characterization and X-ray Crystal Structures of SbCl₄⁺Sb(OTeF₅)₆^- and SbBr₄⁺Sb(OTeF₅)₆^-

et al. 1996

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“…The C−O bond lengths are similar to those in C(OH) 3 + (1.231(4) Å), CH 3 C(OH) 2 + (1.265(6), 1.272(6) Å; 1.261(7), 1.273(7) Å 30 ), and HC(OH) 2 + (1.239(6), 1.255(5) Å) . As expected for a positively charged isoelectronic species, the C−O bond lengths are shorter than the B−O bond lengths of B(OTeF 5 ) 3 (1.358(6) Å), and the C−O−Te bond angles, which range from 125.7(7) to 132.4(9)°, are similar to those in B(OTeF 5 ) 3 (132.3(4)°) . The bond lengths and bond angles in the OTeF 5 groups are in good agreement with those observed for the OTeF 5 groups of the Sb(OTeF 5 ) 6 - anion and other OTeF 5 derivatives 41,54 and require no further comment.…”

Section: Resultssupporting

confidence: 67%

“…The C(OTeF 5 ) 3 + cation is isoelectronic and isostructural with the known B(OTeF 5 ) 3 molecule . To our knowledge, the C(OTeF 5 ) 3 + cation is only the second example of a trioxygen-substituted carbocation to have been isolated and characterized in the solid state by X-ray crystallography, the first being the AsF 6 - salt of the trigonal planar acidium ion of carbonic acid, C(OH) 3 + .…”

Section: Resultsmentioning

confidence: 85%

“…Moreover, the small distortions of the F−Te−F bond angles from 90° in C(OTeF 5 ) 3 + and the near-regular OTeF 5 groups observed for B(OTeF 5 ) 3 are also reproduced by the calculations.

5 Experimental (left) and calculated (right) geometries for (a) the C(OTeF 5 ) 3 + cation and (b) the B(OTeF 5 ) 3 molecule (experimental structure from ref ). …”

Section: Resultsmentioning

confidence: 99%

“…Experimental (left) and calculated (right) geometries for (a) the C(OTeF 5 ) 3 + cation and (b) the B(OTeF 5 ) 3 molecule (experimental structure from ref ). …”

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

The Syntheses of Carbocations by Use of the Noble-Gas Oxidant, [XeOTeF₅][Sb(OTeF₅)₆]: The Syntheses and Characterization of the CX₃⁺ (X = Cl, Br, OTeF₅) and CBr(OTeF₅)₂⁺ Cations and Theoretical Studies of CX₃⁺ and BX₃ (X = F, Cl, Br, I, OTeF₅)

et al. 2004

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The CCl(3)(+) and CBr(3)(+) cations have been synthesized by oxidation of a halide ligand of CCl(4) and CBr(4) at -78 degrees C in SO(2)ClF solvent by use of [XeOTeF(5)][Sb(OTeF(5))(6)]. The CBr(3)(+) cation reacts further with BrOTeF(5) to give CBr(OTeF(5))(2)(+), C(OTeF(5))(3)(+), and Br(2). The [XeOTeF(5)][Sb(OTeF(5))(6)] salt was also found to react with BrOTeF(5) in SO(2)ClF solvent at -78 degrees C to give the Br(OTeF(5))(2)(+) cation. The CCl(3)(+), CBr(3)(+), CBr(OTeF(5))(2)(+), C(OTeF(5))(3)(+), and Br(OTeF(5))(2)(+) cations and C(OTeF(5))(4) have been characterized in SO(2)ClF solution by (13)C and/or (19)F NMR spectroscopy at -78 degrees C. The X-ray crystal structures of the CCl(3)(+), CBr(3)(+), and C(OTeF(5))(3)(+) cations have been determined in [CCl(3)][Sb(OTeF(5))(6)], [CBr(3)][Sb(OTeF(5))(6)].SO(2)ClF, and [C(OTeF(5))(3)][Sb(OTeF(5))(6)].3SO(2)ClF at -173 degrees C. The CCl(3)(+) and CBr(3)(+) salts were stable at room temperature, whereas the CBr(n)(OTeF(5))(3-n)(+) salts were stable at 0 degrees C for several hours. The cations were found to be trigonal planar about carbon, with the CCl(3)(+) and CBr(3)(+) cations showing no significant interactions between their carbon atoms and the fluorine atoms of the Sb(OTeF(5))(6)(-) anions. In contrast, the C(OTeF(5))(3)(+) cation interacts with an oxygen of each of two SO(2)ClF molecules by coordination along the three-fold axis of the cation. The solid-state Raman spectra of the Sb(OTeF(5))(6)(-) salts of CCl(3)(+) and CBr(3)(+) have been obtained and assigned with the aid of electronic structure calculations. The CCl(3)(+) cation displays a well-resolved (35)Cl/(37)Cl isotopic pattern for the symmetric CCl(3) stretch. The energy-minimized geometries, natural charges, and natural bond orders of the CCl(3)(+), CBr(3)(+), CI(3)(+), and C(OTeF(5))(3)(+) cations and of the presently unknown CF(3)(+) cation have been calculated using HF and MP2 methods have been compared with those of the isoelectronic BX(3) molecules (X = F, Cl, Br, I, and OTeF(5)). The (13)C and (11)B chemical shifts for CX(3)(+) (X = Cl, Br, I) and BX(3) (X = F, Cl, Br, I) were calculated by the GIAO method, and their trends were assessed in terms of paramagnetic contributions and spin-orbit coupling.

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Pentafluorooxotellurates(VI)

Sladky¹,

Schack

1986

Inorganic Syntheses

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Tris[pentafluorotellurato(VI)]boron(III)

Cited by 13 publications

References 7 publications

Tetrachloro- and Tetrabromostibonium(V) Cations: Raman and ¹⁹F, ¹²¹Sb, and ¹²³Sb NMR Spectroscopic Characterization and X-ray Crystal Structures of SbCl₄⁺Sb(OTeF₅)₆^- and SbBr₄⁺Sb(OTeF₅)₆^-

Tetrachloro- and Tetrabromostibonium(V) Cations: Raman and ¹⁹F, ¹²¹Sb, and ¹²³Sb NMR Spectroscopic Characterization and X-ray Crystal Structures of SbCl₄⁺Sb(OTeF₅)₆^- and SbBr₄⁺Sb(OTeF₅)₆^-

The Syntheses of Carbocations by Use of the Noble-Gas Oxidant, [XeOTeF₅][Sb(OTeF₅)₆]: The Syntheses and Characterization of the CX₃⁺ (X = Cl, Br, OTeF₅) and CBr(OTeF₅)₂⁺ Cations and Theoretical Studies of CX₃⁺ and BX₃ (X = F, Cl, Br, I, OTeF₅)

Pentafluorooxotellurates(VI)

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Tris[pentafluorotellurato(VI)]boron(III)

Cited by 13 publications

References 7 publications

Tetrachloro- and Tetrabromostibonium(V) Cations: Raman and 19F, 121Sb, and 123Sb NMR Spectroscopic Characterization and X-ray Crystal Structures of SbCl4+Sb(OTeF5)6- and SbBr4+Sb(OTeF5)6-

Tetrachloro- and Tetrabromostibonium(V) Cations: Raman and 19F, 121Sb, and 123Sb NMR Spectroscopic Characterization and X-ray Crystal Structures of SbCl4+Sb(OTeF5)6- and SbBr4+Sb(OTeF5)6-

The Syntheses of Carbocations by Use of the Noble-Gas Oxidant, [XeOTeF5][Sb(OTeF5)6]: The Syntheses and Characterization of the CX3+ (X = Cl, Br, OTeF5) and CBr(OTeF5)2+ Cations and Theoretical Studies of CX3+ and BX3 (X = F, Cl, Br, I, OTeF5)

Pentafluorooxotellurates(VI)

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Tetrachloro- and Tetrabromostibonium(V) Cations: Raman and ¹⁹F, ¹²¹Sb, and ¹²³Sb NMR Spectroscopic Characterization and X-ray Crystal Structures of SbCl₄⁺Sb(OTeF₅)₆^- and SbBr₄⁺Sb(OTeF₅)₆^-

Tetrachloro- and Tetrabromostibonium(V) Cations: Raman and ¹⁹F, ¹²¹Sb, and ¹²³Sb NMR Spectroscopic Characterization and X-ray Crystal Structures of SbCl₄⁺Sb(OTeF₅)₆^- and SbBr₄⁺Sb(OTeF₅)₆^-

The Syntheses of Carbocations by Use of the Noble-Gas Oxidant, [XeOTeF₅][Sb(OTeF₅)₆]: The Syntheses and Characterization of the CX₃⁺ (X = Cl, Br, OTeF₅) and CBr(OTeF₅)₂⁺ Cations and Theoretical Studies of CX₃⁺ and BX₃ (X = F, Cl, Br, I, OTeF₅)