Trimethylsilyl fluoride


Reaction thermochemistry data

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Data compilation copyright by the U.S. Secretary of Commerce on behalf of the U.S.A. All rights reserved.

Data compiled as indicated in comments:
B - John E. Bartmess
M - Michael M. Meot-Ner (Mautner) and Sharon G. Lias

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Individual Reactions

Fluorine anion + Trimethylsilyl fluoride = (Fluorine anion • Trimethylsilyl fluoride)

By formula: F- + C3H9FSi = (F- • C3H9FSi)

Quantity Value Units Method Reference Comment
Δr38.2 ± 2.0kcal/molIMRELarson and McMahon, 1985gas phase; These relative affinities are ca. 10 kcal/mol weaker than threshold values (see Wenthold and Squires, 1995) for donors greater than ca. 27 kcal/mol in free energy. This discrepancy has not yet been resolved, though the stronger value appears preferable.; B,M
Δr<54. ± 10.kcal/molIMRBMurphy and Beauchamp, 1977gas phase; B
Quantity Value Units Method Reference Comment
Δr22.cal/mol*KN/ALarson and McMahon, 1985gas phase; switching reaction,Thermochemical ladder(F-)H2O, Entropy change calculated or estimated; Arshadi, Yamdagni, et al., 1970; M
Quantity Value Units Method Reference Comment
Δr31.6 ± 2.0kcal/molIMRELarson and McMahon, 1985gas phase; These relative affinities are ca. 10 kcal/mol weaker than threshold values (see Wenthold and Squires, 1995) for donors greater than ca. 27 kcal/mol in free energy. This discrepancy has not yet been resolved, though the stronger value appears preferable.; B,M

C3H8FSi- + Hydrogen cation = Trimethylsilyl fluoride

By formula: C3H8FSi- + H+ = C3H9FSi

Quantity Value Units Method Reference Comment
Δr388.5 ± 4.7kcal/molG+TSAllison and McMahon, 1990gas phase; Between H2O, HO.; B
Quantity Value Units Method Reference Comment
Δr380.2 ± 4.6kcal/molIMRBAllison and McMahon, 1990gas phase; Between H2O, HO.; B

Gas Chromatography

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Data compilation copyright by the U.S. Secretary of Commerce on behalf of the U.S.A. All rights reserved.

Data compiled by: NIST Mass Spectrometry Data Center, William E. Wallace, director

Normal alkane RI, non-polar column, temperature ramp

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Column type Active phase I Reference Comment
CapillaryOV-101437.Zenkevich, 200525. m/0.20 mm/0.10 μm, N2/He, 6. K/min; Tstart: 50. C; Tend: 250. C

Normal alkane RI, non-polar column, custom temperature program

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Column type Active phase I Reference Comment
CapillarySE-52416.van Langenhove and Schamp, 1986Column length: 100. m; Column diameter: 0.50 mm; Program: not specified

References

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Data compilation copyright by the U.S. Secretary of Commerce on behalf of the U.S.A. All rights reserved.

Larson and McMahon, 1985
Larson, J.W.; McMahon, T.B., Fluoride and chloride affinities of the main group oxides, fluorides, oxofluorides, and alkyls. Quantitative scales of lewis acidities from ICR halide exchange equilibria, J. Am. Chem. Soc., 1985, 107, 766. [all data]

Wenthold and Squires, 1995
Wenthold, P.G.; Squires, R.R., Bond dissociation energies of F2(-) and HF2(-). A gas-phase experimental and G2 theoretical study, J. Phys. Chem., 1995, 99, 7, 2002, https://doi.org/10.1021/j100007a034 . [all data]

Murphy and Beauchamp, 1977
Murphy, M.K.; Beauchamp, J.L., Methyl and Fluorine Substituent Effects on the Gas Phase Lewis Acidities of Silanes by ICR Spectroscopy, J. Am. Chem. Soc., 1977, 99, 15, 4992, https://doi.org/10.1021/ja00457a017 . [all data]

Arshadi, Yamdagni, et al., 1970
Arshadi, M.; Yamdagni, R.; Kebarle, P., Hydration of Halide Negative Ions in the Gas Phase. II. Comparison of Hydration Energies for the Alkali Positive and Halide Negative Ions, J. Phys. Chem., 1970, 74, 7, 1475, https://doi.org/10.1021/j100702a014 . [all data]

Allison and McMahon, 1990
Allison, C.E.; McMahon, T.B., How Strong is the Si=C Bond in Fluoro- and Methyl Substituted Silaethylenes? An Experimental Determination of Pi Bond Strengths, J. Am. Chem. Soc., 1990, 112, 5, 1672, https://doi.org/10.1021/ja00161a002 . [all data]

Zenkevich, 2005
Zenkevich, I.G., Experimentally measured retention indices., 2005. [all data]

van Langenhove and Schamp, 1986
van Langenhove, H.; Schamp, N., Identification of Volatiles in the Head Space of Acid-Treated Phosphate Rock by Gas Chromatography-Mass Spectromety, J. Chromatogr., 1986, 351, 65-75, https://doi.org/10.1016/S0021-9673(01)83473-7 . [all data]


Notes

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