Preparation and characterization of some monofluoroselenite and -tellurite compounds

Milne, J. B.

doi:10.1021/ic50190a052

Cited by 10 publications

(5 citation statements)

References 19 publications

(7 reference statements)

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“…Since its four lower frequency modes have relatively similar frequencies and intensities, we have calculated its vibrational spectra at the CCSD(T)/augcc-pVDZ and B3LYP/aug-cc-pVTZ levels of theory (Table 8) to verify the previously proposed assignments [16]. It was found that our current Raman spectrum for CsSeO 2 F was in good agreement with that previously reported and that the previously proposed assignments are also correct.…”

Section: Vibrational Spectrasupporting

confidence: 80%

“…The vibrational spectra of the SeO 2 F À anion have previously been reported and analyzed in detail [16]. Since its four lower frequency modes have relatively similar frequencies and intensities, we have calculated its vibrational spectra at the CCSD(T)/augcc-pVDZ and B3LYP/aug-cc-pVTZ levels of theory (Table 8) to verify the previously proposed assignments [16].…”

Section: Vibrational Spectramentioning

confidence: 60%

“…It was found that our current Raman spectrum for CsSeO 2 F was in good agreement with that previously reported and that the previously proposed assignments are also correct. The largest deviations between the calculated and observed frequencies are attributed in part to anion association and solid state effects, because the deviations become smaller with increasing cation size and for solutions of the salts in either CH 3 CN or (CH 3 ) 2 SO [16]. We note that the SeO 2 stretching frequencies are calculated to be closer to each other than was experimentally observed and that their order should be reversed with the SeO 2 antisymmetric stretching frequency being higher than the symmetric one.…”

Section: Vibrational Spectramentioning

confidence: 98%

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Selenium(IV) fluoride and oxofluoride anions

Dixon

Haiges

Hopfinger

et al. 2010

Journal of Fluorine Chemistry

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Section: Vibrational Spectrasupporting

confidence: 80%

Section: Vibrational Spectramentioning

confidence: 60%

Section: Vibrational Spectramentioning

confidence: 98%

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Selenium(IV) fluoride and oxofluoride anions

Dixon

Haiges

Hopfinger

et al. 2010

Journal of Fluorine Chemistry

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“…Theoretical studies appear to be necessary in order to reach an unambiguous assignment of the absorptions. However, the spectra do not agree with the spectra given by Milne [16] who has claimed to have synthesized KTeO 2 F. …”

Section: Vibrational Spectroscopy and Thermal Analysiscontrasting

confidence: 75%

Trimeric Anions in KTeO2F

Keßler

Jansen

2000

Eur. J. Inorg. Chem.

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“…There is significant interest in the thermochemical properties including bond dissociation energies (BDEs) of compounds of the main group elements of the second- and higher-rows. , There have been a number of structural and spectroscopic studies of the binary selenium fluorides SeF 4 , − SeF 5 – , ,, and SeF 6 2– , , and the selenium oxofluorides including SeOF 2 , ,− SeO 2 F – , ,− and SeOF 3 – . ,− Octahedral SeF 6 has been studied extensively, and its geometry, heat of formation, vibrational frequencies, and 77 Se NMR chemical shifts − have been reported. The crystal structure of a compound of the form RSeF with R a phenyl ring with large bulky substituents was just reported .…”

Section: Introductionmentioning

confidence: 99%

Thermochemical Properties of Selenium Fluorides, Oxides, and Oxofluorides

Jackson

Dixon

2012

Inorg. Chem.

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The bond dissociation energies (BDEs), fluoride and fluorocation affinities, and electron affinities of SeF(n) (n = 1-6), SeOF(n) (n = 0-4), and SeO(2)F(n) (n = 0-2) have been predicted with coupled cluster CCSD(T) theory extrapolated to the complete basis set limit. To achieve near chemical accuracy, additional corrections were added to the complete basis set binding energies based on frozen core coupled cluster theory energies. These included corrections for core-valence effects, scalar relativistic effects, for first-order atomic spin-orbit effects, and vibrational zero point energies. The adiabatic BDEs contain contributions from product reorganization energies and, therefore, can be much smaller than the diabatic BDEs and can vary over a wide range. For thermochemical calculations, the adiabatic values must be used, whereas for bond strength and kinetic considerations, the diabatic values should be used when only small displacements of the atoms without change of the geometry of the molecule are involved. The adiabatic Se-F BDEs of SeF(n) (n = 1-6) are SeF(6) = 90, SeF(5) = 27, SeF(4) = 93, SeF(3) = 61, SeF(2) = 86, and SeF = 76 kcal/mol, and the corresponding diabatic values are SeF(6) = 90, SeF(5) = 88, SeF(4) = 93, SeF(3) = 74, SeF(2) = 86, and SeF = 76 kcal/mol. The adiabatic Se-O BDEs of SeO(n) (n = 1-3), SeOF(n) (n = 1-4), and SeO(2)F(n) (n = 1,2) range from 23 to 107 kcal/mol, whereas the diabatic ones range from 62 to 154 kcal/mol. The adiabatic Se-F BDEs of SeOF(n) (n = 1-4) and SeO(2)F(n) (n = 1,2) range from 20 to 88 kcal/mol, whereas the diabatic ones range from 73 to 112 kcal/mol. The fluoride affinities of SeF(n), (n = 1-6), SeO(n), (n = 1-3), SeOF(n), (n = 1-4), and SeO(2)F(n) (n = 1,2) range from 15 to 121 kcal/mol, demonstrating that the Lewis acidity of these species covers the spectrum from very weak (SeF(6)) to very strong (SeO(3)) acids. The electron affinities which are a measure of the oxidizing power of a species, span a wide range from 1.56 eV in SeF(4) to 5.16 eV in SeF(5) and for the free radicals are much higher than for the neutral molecules. Another interesting feature of these molecules and ions stems from the fact that many of them possess both a Se free valence electron pair and a free unpaired valence electron, raising the questions of their preferred location and their influence on the Se-F and Se═O bond strengths.

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Preparation and characterization of some monofluoroselenite and -tellurite compounds

Cited by 10 publications

References 19 publications

Selenium(IV) fluoride and oxofluoride anions

Selenium(IV) fluoride and oxofluoride anions

Trimeric Anions in KTeO2F

Thermochemical Properties of Selenium Fluorides, Oxides, and Oxofluorides

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