Radicals from tributyl phosphate decomposition: a combined electron paramagnetic resonance spectroscopic and computational chemistry investigation†

Abstract

The radiation- and chemically-induced radicals from tributyl phosphate (TBP) have been characterized by EPR spectroscopy and theoretical calculations. The yield of X-ray-generated TBP radicals measured by a PBN spin trap is 0.22 μmol J⁻¹ (2.1 radicals/100 eV) at room temperature (298 K). The EPR spectra obtained by irradiating TBP with an electron beam at 77 K are in close agreement with literature data for samples irradiated with gamma- and X-rays [https://doi.org/10.1007/BF02165504, https://doi.org/10.1016/1359-0197(89)90319-6]. Possible conformers of alkyl-type, TBP-derived radicals were analyzed by Density Functional Theory calculations. The main contribution to the experimental spectrum at 77 K is shown to be made by a conformer of the CH₃˙CHCH₂-radical, which contains all carbon atoms of the butyl group in the same plane. The EPR spectra of TBP radicals induced by the OH radical in aqueous solution were measured for the first time using a continuous flow system. The formation of the alkyl-type TBP radicals CH₃˙CHCH₂-, ˙CH₂CH₂-, and -CH₂˙CHO- in the ratio of 5/4/1 was detected; their spectral assignment was based on quantum chemical calculations with rotational averaging of HFC constants for the corresponding beta- and alpha-protons.