Determination of thermodynamic functions by means of infrared spectroscopy. Complex formation in phenol-aliphatic sulfide and phenol-aliphatic sulfoxide systems

The hydrogen bond acceptor (HBA) strength of 31 tetrahedral sulfur bases (thioethers, thiols, disulfides) has been measured by IR spectrometry from: (i) their 1:1 complexation constants with 4-fluorophenol in CCl4 at 25 °C (the pKHB scale); (ii) their HB enthalpies; and (iii) the frequency shifts, Δν(OH), of the ν(OH) band of 4-fluorophenol hydrogen bonded to sulfur. The comparison of the pKHB, ΔH°, and Δν(OH) scales points to their distinctive features. The HBA strength depends on: (i) the nature of the atomic site: oxygen bases are always stronger than sulfur bases, in agreement with the hard and soft acids and bases principle; (ii) the functionality of this atom (for sulfur bases: phosphine sulfur > thioamide > thioketone > thioether > thiol > isothiocyanate ~ disulfide); and (iii) the substituent effects on the function. The main substituent effects are: (i) the polarizability effect of alkyl groups; (ii) the field-inductive effect; (iii) the resonance effect; and (iv) the cyclization effect, which changes the percentage of the s character of sulfur lone pairs. In addition to the attachment to the sulfur atom, IR spectra show the attachment of 4-fluorophenol to the chlorine of MeSCH2Cl and MeSCH2CH2Cl, and the interaction to the π cloud of PhSMe, Ph2S, PhCH2SMe, and EtSCH=CH2. Key words: hydrogen bond, thioethers, thiols, disulfides, pKHB scale.

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Determination of thermodynamic functions by means of infrared spectroscopy. Complex formation in phenol-aliphatic sulfide and phenol-aliphatic sulfoxide systems

Cited by 2 publications

References 4 publications

Polarization effect in radical cations and H-complexes

Polarization effect in radical cations and H-complexes

Échelles pK_HBet enthalpique du pouvoir accepteur de liaison hydrogène de thioéthers, thiols et disulfures

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Determination of thermodynamic functions by means of infrared spectroscopy. Complex formation in phenol-aliphatic sulfide and phenol-aliphatic sulfoxide systems

Cited by 2 publications

References 4 publications

Polarization effect in radical cations and H-complexes

Polarization effect in radical cations and H-complexes

Échelles pKHBet enthalpique du pouvoir accepteur de liaison hydrogène de thioéthers, thiols et disulfures

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Échelles pK_HBet enthalpique du pouvoir accepteur de liaison hydrogène de thioéthers, thiols et disulfures