1 research outputs found
Manifesting Direction-Specific Complexation in [HFIP<sub>–H</sub>·H<sub>2</sub>O<sub>2</sub>]<sup>−</sup>: Exclusive Formation of a High-Lying Conformation
Size-selective, negative ion photoelectron spectroscopy
in conjunction
with quantum chemical calculations is employed to investigate the
geometric and electronic structures of a protype system in catalytic
olefin epoxidation research, that is, deprotonated hexafluoroisopropanol
([HFIP–H]−) complexed with hydrogen
peroxide (H2O2). Spectral assignments and molecular
electrostatic surface analyses unveil a surprising prevalent existence
of a high-lying isomer with asymmetric dual hydrogen-bonding configuration
that is preferably formed driven by influential direction-specific
electrostatic interactions upon H2O2 approaching
[HFIP–H]− anion. Subsequent inspections
of molecular orbitals, charge, and spin density distributions indicate
the occurrence of partial charge transfer from [HFIP–H]− to H2O2 upon hydrogen-bonding
interactions. Accompanied with electron detachment, a proton transfer
occurs to form the neutral complex of [HFIP·HOO•] structure. This work conspicuously illustrates the importance of
directionality encoded in intermolecular interactions involving asymmetric
and complex molecules, while the produced hydroperoxyl radical HOO• offers a possible new pathway in olefin epoxidation
chemistry