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Matrix-Isolation Infrared Spectroscopy of Organic Phosphates

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Matrix-isolation infrared spectra of trimethyl phosphate (TMP), triethyl phosphate (TEP), and tri-n-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 C 3, conformer relative to the C 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.

Keywords: Conformations; FT-IR; Infrared; Matrix-isolation; Organic phosphates; Tri-n-butyl phosphate; Triethyl phosphate; Trimethyl phosphate

Document Type: Research Article


Affiliations: Chemical Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102, India

Publication date: January 1, 1994

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