2015
DOI: 10.1002/cphc.201500177
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Negative Hyperconjugation versus Electronegativity: Vibrational Spectra of Free Fluorinated Alkoxide Ions in the Gas Phase

Abstract: CO stretching frequencies of free, gaseous, fluorinated alkoxide ions shift substantially to the blue, relative to those of corresponding alcohols complexed with ammonia. Free α-fluorinated ions, pentafluoroethoxide and heptafluoroisopropoxide anions, display further blue shifts relative to cases with only β-fluorination, providing experimental evidence for fluorine negative hyperconjugation. DFT analysis with the atoms in molecules (AIM) method confirms an increase in CO bond order for the α-fluorinated ions,… Show more

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Cited by 11 publications
(14 citation statements)
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“…By contrast, the most intense absorptions in the fingerprint region, the CO stretches,a re not badly fitted by the unscaled anharmonic calculations,predicted at 1204 cm À1 for 2 and 1235 cm À1 for 2-d.N ote that the shift to the blue with deuteration conforms to experiment. CO stretches are also not badly predicted by calculation for the other anions in Table 1, as our prior paper [6] reports for ions 1 and 4 and also found here for ions 3, 5,a nd 6 (predicted at 1199, 1181, and 1161 cm À1 ,respectively).…”
Section: Angewandte Chemiesupporting
confidence: 87%
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“…By contrast, the most intense absorptions in the fingerprint region, the CO stretches,a re not badly fitted by the unscaled anharmonic calculations,predicted at 1204 cm À1 for 2 and 1235 cm À1 for 2-d.N ote that the shift to the blue with deuteration conforms to experiment. CO stretches are also not badly predicted by calculation for the other anions in Table 1, as our prior paper [6] reports for ions 1 and 4 and also found here for ions 3, 5,a nd 6 (predicted at 1199, 1181, and 1161 cm À1 ,respectively).…”
Section: Angewandte Chemiesupporting
confidence: 87%
“…Recently these laboratories reported density functional (DFT) calculations that predict ar ed shift of hundreds of wavenumbers for the a-CH stretching frequencies of free alkoxide ions relative to their alkali metal salts. [6] Here we present experimental confirmation of those predictions using inter alia the free electron laser for infrared experiments (FELIX). Some of these CH stretches occur even lower than the lowest CH stretch of protonated methane (CH 5 + ).…”
supporting
confidence: 62%
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“…Theoretical calculations predicted that the C(2)ÀHs tretching band in the isopropoxy anions is red-shifted by several hundreds of wavenumbers with respect to the position of the usual aliphatic CÀHs tretching bands. [11] This extreme red-shift occurs upon isopropanol deprotonation. The oxygen anion forms ap artial double bond with the C(2) carbon atom.…”
Section: What Is the Effect Of Charge?mentioning
confidence: 99%
“…[8] The negative hyperconjugation is one of the important concepts in organic chemistry and has been extensively studied so far. [9][10][11][12][13][14][15][16][17][18][19][20][21][22] An excellent linear correlation between the GA values and the corrected number of fluorine atoms contained in the fluorinated alkyl group (R f ) was observed for the polyfluorinated alkanes having no fluorine atom at β-position of the conjugate acid's anion center. On the basis of this finding, the extent of β-fluorine negative hyperconjugation involved in the acidity was evaluated quantitatively.…”
Section: Introductionmentioning
confidence: 99%