Manifesting Direction-Specific Complexation in [HFIP -H ·H 2 O 2 ] - : Exclusive Formation of a High-Lying Conformation.
Jia HanLei WangWenjin CaoQinqin YuanXiaoguo ZhouShilin LiuXue-Bin WangPublished in: The journal of physical chemistry letters (2022)
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 (H 2 O 2 ). 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 H 2 O 2 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 H 2 O 2 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.
Keyphrases
- hydrogen peroxide
- density functional theory
- molecular dynamics simulations
- single molecule
- molecular dynamics
- nitric oxide
- solid state
- high resolution
- risk assessment
- monte carlo
- magnetic resonance imaging
- ionic liquid
- room temperature
- electron transfer
- crystal structure
- energy transfer
- computed tomography
- drug discovery
- transition metal
- contrast enhanced