An Infrared Spectroscopic Study of Hydrogen Bonds. The Liquid-Liquid Interaction of Solvents with Trimethylsilanol

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An infrared spectroscopic study of the hydrogen-bonding interaction of binary solvents (S1–S2) with trimethylsilanol has been made, where CCl4 is used as S1 and the aromatic hydrocarbons and the O- and N-containing solvents, as S2. On the basis of the findings on the O–H frequency shifts (ΔνOH) of trimethylsilanol, the equilibrium constants (K) and the preferential coordination constants (α1−2) of hydrogen-bond formation, the difference in the O–H···π and the O–H···n hydrogen-bonding interactions has been discussed. The free-energy changes (−ΔG) were found to be better related to the apparent half-widths (Δν1⁄2) of the O–H bands than the ΔνOH. The ΔνOH of trimethylsilanol caused by the interaction with the solvent was in good correlation with the donor number defined as the heat of mixing of the solvent with antimony(V) chloride. From the linear relationship between the ΔνOH of trimethylsilanol and the ΔνSOH of the surface silanol caused by the gas-phase adsorption on silica gel, it was also found that the proton-donating power of the surface silanol was considerably larger than that of trimethylsilanol and was nearly equal to that of p-nitrophenol. There existed a linear relationship through the point of origin between the α1−2 and the separation factors (αS1−2) in the liquid-phase adsorption on the silica gel surface.
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