A reassignment of the vibrational fundamentals of sulfuryl chloride fluoride

Craig, Norman C.; Futamura, Kenichi

doi:10.1016/0584-8539(89)80049-2

Cited by 3 publications

(2 citation statements)

References 9 publications

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“…The experimental and calculated frequencies for SO 2 ClF, XeOTeF 5 + , and XeOTeF 5 + ·SO 2 ClF and the assignments for XeOTeF 5 + · SO 2 ClF are also provided in Table . The present assignments for SO 2 ClF are in agreement with those reported for the neat liquid, but are now more precisely described. The present assignments for XeOTeF 5 + reproduce the published assignments for this cation .…”

Section: Resultssupporting

confidence: 90%

“…The Raman assignments for the adduct-cation, XeOTeF 5 + · SO 2 ClF, were made by comparison with the calculated frequencies and were also guided by previous vibrational assignments for SO 2 ClF and XeOTeF 5 + , ,, as well as by more recent detailed assignments provided in the Supporting Information (Tables S3 and S4, respectively). Calculations of the vibrational frequencies were carried out at the HF and DFT levels of theory using Stuttgart and (SDB-)cc-PVTZ basis sets, but only the DFT results are reported in Table (also see Supporting Information, Table S5).…”

Section: Resultsmentioning

confidence: 99%

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Synthesis, Structural Characterization, and Computational Study of the Strong Oxidant Salt [XeOTeF₅][Sb(OTeF₅)₆]·SO₂ClF

et al. 2004

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The strong oxidant salt [XeOTeF(5)][Sb(OTeF(5))(6)].SO(2)ClF has been synthesized by reaction of stoichiometric amounts of Xe(OTeF(5))(2) and Sb(OTeF(5))(3) in SO(2)ClF solution at -78 degrees C and characterized in SO(2)ClF solution by low-temperature (17)O, (19)F, (121)Sb, (125)Te, and (129)Xe NMR spectroscopy, showing the Xe...O donor-acceptor bond XeOTeF(5)(+).SO(2)ClF adduct-cation to be labile at temperatures as low as -80 degrees C. The salt crystallizes from SO(2)ClF as [XeOTeF(5)][Sb(OTeF(5))(6)].SO(2)ClF, and the low-temperature crystal structure was obtained: triclinic, P, a = 9.7665(5) A, b = 9.9799(4) A, c = 18.5088(7) A, alpha = 89.293(2) degrees , beta = 82.726(2) degrees , gamma = 87.433(3) degrees , V = 1787.67(13) A(3), Z = 2, and R(1) = 0.0.0451 at -173 degrees C. Unlike MF(6)(-) in [XeF][MF(6)] (e.g., M = As, Sb, Bi) and [XeOTeF(5)][AsF(6)], the Sb(OTeF(5))(6)(-) anion is significantly less basic and does not interact with the coordinately unsaturated xenon(II) cation. Rather, the XeOTeF(5)(+) cation and weak Lewis base, SO(2)ClF, interact by coordination of an oxygen atom of SO(2)ClF to xenon [Xe...O, 2.471(5) A]. The XeOTeF(5)(+).SO(2)ClF adduct-cation has also been studied by low-temperature Raman spectroscopy, providing frequencies that have been assigned to adducted SO(2)ClF. The solid-state Raman spectra of XeOTeF(5)(+).SO(2)ClF and Sb(OTeF(5))(6)(-) have been assigned with the aid of electronic structure calculations. In addition to optimized geometries and vibrational frequencies, theoretical data, including gas-phase donor-acceptor bond energies, natural bond orbital (NBO) analyses, and topological analyses based on electron localization functions (ELF), provide descriptions of the bonding in XeOTeF(5)(+).SO(2)ClF and related systems. The quantum mechanical calculations provided consistent trends for the relative strengths of the Xe...O donor-acceptor bond in XeOTeF(5)(+).SO(2)ClF and ion-pair bonds in [XeL][MF(6)] (L = F, OTeF(5); M = As, Sb), with the Xe...O bond of XeOTeF(5)(+).SO(2)ClF being the weakest in the series.

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Section: Resultssupporting

confidence: 90%

Section: Resultsmentioning

confidence: 99%

Synthesis, Structural Characterization, and Computational Study of the Strong Oxidant Salt [XeOTeF₅][Sb(OTeF₅)₆]·SO₂ClF

et al. 2004

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A scaled quantum mechanical force field for the sulfuryl halides

Fernández

Varetti

2005

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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Microwave spectrum of sulfuryl chloride fluoride, SO₂ClF: structure, hyperfine constants and harmonic force field

Müller¹,

Gerry²

1994

J. Chem. Soc., Faraday Trans.

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The pure rotational spectrum of sulfuryl chloride fluoride, SO,CIF, has been investigated in the frequency range 5.6-24.0 GHz using a pulsed molecular beam microwave Fourier-transform spectrometer. Between 48 and 170 lines of 8 to 26 rotational transitions have been observed for the six isotopomers SO,CIF, SO, 37CIF, 34S0,CIF, 34S0, 37CIF, SO'80CIF and SO " 0 37CIF (unlabelled atoms indicate l60, "F, 32S and 35CI) in natural isotopic abundance. The rotational and quartic centrifugal distortion constants have been determined. ro I T A P and r,-type structural parameters have been evaluated. A harmonic force field has been calculated to derive ground-state average and estimated equilibrium geometries. The description of the normal modes in terms of internal coordinates is discussed. Chlorine and fluorine hyperfine structures have been resolved, allowing quadrupole coupling (including zbc for the isotopomers containing " 0 ) and spin-rotation constants to be determined. Variations in the chlorine quadrupole coupling constants with different isotopomers have allowed the CI quadrupole tensor to be diagonalized and indicate that its z-axis coincides with the SCI bond.Although sulfuryl chloride fluoride, SO,ClF, has been known for more than 50 years,' there is only one study, by Holt and Gerry, reporting its structure in the gas phase., Using a conventional Stark modulated microwave spectrometer, they determined rotational constants, chlorine quadrupole coupling constants and an effective distortion constant for each of the two most abundant isotopomers, S0,ClF and SO, 37ClF (unlabelled atoms indicate l60, 19F, 32S and 35Cl). By assuming values for r ( S 0 ) and L(C1SF) from a comparison with the related molecules sulfuryl fluoride, SO,F,, and sul-fury1 chloride, S02C12, they were able to derive the remaining geometrical parameters.Recently Gombler investigated 32/34S isotopic shifts of the "F NMR frequency of sulfur-and fluorine-containing comp o u n d ~. ~ From these results he suggested that the SF bond in S 0 2 F 2 should be longer than that in SO,ClF, in contrast to the conclusions from the microwave studies. More recently a single-crystal X-ray diffraction study of S0,XY (X, Y = C1, F) at low temperatures has yielded the precise geometrical parameters of these compounds in the solid state.4Raman and IR spectra have also been re~orded.'.~ In addition, Pfeiffer obtained a force field of S0,ClF by transferring force constants and structural parameters from S02C1, and S02F2.7 These force constants reproduced most of the observed vibrational wavenumbers moderately well. Better agreement was obtained when the assignments of two pairs of fundamentals in ref. 5 were exchanged. In addition, the earlier assignment of the v6 band' was rejected and it was assumed that this fundamental is overlapped by v9. The assignments of Pfeiffer have been confirmed in a recent reinvestigation of the Raman and IR spectra.'At room temperature the microwave spectrum of S0,ClF is very dense, with many transitions between rotational levels at ...

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A reassignment of the vibrational fundamentals of sulfuryl chloride fluoride

Cited by 3 publications

References 9 publications

Synthesis, Structural Characterization, and Computational Study of the Strong Oxidant Salt [XeOTeF₅][Sb(OTeF₅)₆]·SO₂ClF

Synthesis, Structural Characterization, and Computational Study of the Strong Oxidant Salt [XeOTeF₅][Sb(OTeF₅)₆]·SO₂ClF

A scaled quantum mechanical force field for the sulfuryl halides

Microwave spectrum of sulfuryl chloride fluoride, SO₂ClF: structure, hyperfine constants and harmonic force field

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A reassignment of the vibrational fundamentals of sulfuryl chloride fluoride

Cited by 3 publications

References 9 publications

Synthesis, Structural Characterization, and Computational Study of the Strong Oxidant Salt [XeOTeF5][Sb(OTeF5)6]·SO2ClF

Synthesis, Structural Characterization, and Computational Study of the Strong Oxidant Salt [XeOTeF5][Sb(OTeF5)6]·SO2ClF

A scaled quantum mechanical force field for the sulfuryl halides

Microwave spectrum of sulfuryl chloride fluoride, SO2ClF: structure, hyperfine constants and harmonic force field

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Product

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Synthesis, Structural Characterization, and Computational Study of the Strong Oxidant Salt [XeOTeF₅][Sb(OTeF₅)₆]·SO₂ClF

Synthesis, Structural Characterization, and Computational Study of the Strong Oxidant Salt [XeOTeF₅][Sb(OTeF₅)₆]·SO₂ClF

Microwave spectrum of sulfuryl chloride fluoride, SO₂ClF: structure, hyperfine constants and harmonic force field