Abstract

Matrix-isolation infrared spectra of trimethyl phosphate (TMP), triethyl phosphate (TEP), and tri-<i>n</i>-butyl phosphate (TBP), in argon and nitrogen matrices, are reported for the first time. The peak widths of the sharpest features in our matrix-isolated spectra are typically 2 cm^-1, compared with peak widths of 40 cm^-1 seen in liquids for these compounds. Comparison with the vapor-phase spectrum of TMP reported earlier indicates that TMP is trapped in two different conformations in these matrices. Similar spectra were also obtained for TEP. Our matrix-isolated spectra indicate that the intramolecular hydrogen bonding (which is believed to be responsible for the lowering of the P=O frequency in the <i>C</i>₃, conformer relative to the <i>C</i>₃ conformer in these compounds) is stronger in TEP than in TMP. In the case of TBP, the peak widths were larger (8-10 cm^-1) than those obtained for TMP and TEP. This observation is probably due to a distribution of conformers that may be trapped in the matrix, as a result of the increased alkyl chain length in TBP.

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