Manifesting Direction-Specific Complexation in [HFIP–H·H2O2]–: Exclusive Formation of a High-Lying Conformation

Han, Jia; Wang, Lei; Cao, Wenjin; Yuan, Qinqin; Zhou, Xiaoguo; Liu, Shilin; Wang, Xue-Bin

doi:10.1021/acs.jpclett.2c02237

Title: Manifesting Direction-Specific Complexation in [HFIP_–H·H₂O₂]^–: Exclusive Formation of a High-Lying Conformation

Journal Article · Thu Sep 08 00:00:00 UTC 2022 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.2c02237 · OSTI ID:1893855

Han, Jia ^[1]; Wang, Lei ^[1];

^[2]; Yuan, Qinqin ^[3];

^[1]; Liu, Shilin ^[1];

^[2]

Univ. of Science and Technology of China, Hefei (China)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Anhui University, Hefei (China)

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, i.e., 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 hydrogenbonding configuration that is preferably formed driven by influential directionspecific 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. Accompanying with electron detachment, a proton transfer occurs to form the neutral complex of [HFIP•HOO^•] structure. In conclusion, 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.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1893855

Report Number(s):: PNNL-SA-176437

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 36 Vol. 13; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Manifesting Direction-Specific Complexation in [HFIP–H·H2O2]–: Exclusive Formation of a High-Lying Conformation

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Title: Manifesting Direction-Specific Complexation in [HFIP_–H·H₂O₂]^–: Exclusive Formation of a High-Lying Conformation