Abstract
An infrared investigation has been made of relatively weak hydrogen bonded complexes in the gas phase. Wavenumbers and band contours for hydrogen stretching modes have been investigated for O—H ⋯ O complexes formed by methanol, ethanol, propan-2-ol and 2-methylpropan-2-ol with some simple ethers, and also with tetrahydrofuran and 1,4-dioxan. The wavenumber displacements provide a measure of the electron donating abilities of the free ethers, leading to the following series according to increasing basicity : Me2O ≈ 1,4-dioxan < Et2O < THF < Pr1 2O. The bands for the O—H stretching vibration of the alcohol + ether systems are found to be broad but with little or no structure, and this is discussed in terms of the sum-and-difference band theory of broadening. Examples of C—H ⋯ N hydrogen bonding in the gas phase have been detected for trichloromethane + amine systems and frequency displacements are listed. The order of increasing basicity of amines as indicated by these frequency displacements is : NH3 < MeNH2 < Me2N < Me3N.

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