Enantioselective HF loss promoted by resonant two-photon ionization of supersonically expanded (R)-1-phenyl-2,2,2-trifluoroethanol clusters.

(R)-1-Phenyl-2,2,2-trifluoroethanol and its hydrogen bonded adducts with achiral (water, tetrahydrofuran) and chiral solvent mols. ((R)- and (S)-butan-2-ol, (R)- and (S)-3-hydroxy-tetrahydrofuran) have been ionized by resonant two-photon absorption. The presence of photofragments, attributable to the occurrence of a hydrogen fluoride loss reaction, has been interpreted with the aid of theor. predictions at the DFT level of theory with the inclusion of dispersive terms. The HF elimination process takes place by a mechanism involving the preliminary C.alpha.-H hydrogen transfer to an hydroxyl oxygen assisted by the solvent mol. which is followed by extrusion of the HF mol. The calcd. energy barriers depend on the type of solvent as well as on its configuration and are consistent with the obsd. fragmentation ratios.