Microhydration Affects the Competing Product Channels of Oxygen Anion Radical Reacting With Methyl Iodide in Gas Phase
- 1Key Laboratory of Cluster Science of Ministry of Education School of Chemistry and Chemical Engineering Beijing Institute of Technology Beijing China
Abstract
Oxygen anion O− is an important radical in atmospheric, combustion, and biological chemistry. How solvation affects its reaction with haloalkane remains elusive. Here, we report a quantum chemistry calculation on the potential energy profiles of microhydrated O−(H2O)n = 0–3 anions and methyl iodide in the gas phase. The reactive nature of O− leads to multiple product channels, including the halogen abstraction (XA), SN2, proton transfer (PT), hydrogen atom transfer (HAT) pathways, and three post‐HAT pathways, namely the oxygen insertion (OxIn), HAT&PT, and HAT&XA pathways. Higher hydration levels increase both barriers and reaction enthalpies across pathways, but the differential shifts reorder the barrier heights. The OxIn pathway leading to CH2OH + I− is predicted to be the dominant product channel. This is in sharp contrast to conventional closed‐shell ion reactions where the SN2 pathway prevails. Adding water molecules to O− leads to two exothermic SN2 products, CH3O and CH3OH + I−. Remarkably, the formed CH3O, CH2OH, and CH3OH species, with or without water molecules and I− ions, can convert to each other via proton and hydrogen atom transfer. This work elucidates how individual solvent molecules affect the competing radical ion–molecule pathways, offering mechanistic insights into radical‐induced C─H bond activation in hydrocarbons.
Related
- How Fluctuations Control Chiral Symmetry Breaking in Reacting Mixtures of Chiral Molecules
- A Neural Implicit Flow Super-Resolution Approach for Reacting Flows
- Continuum thermodynamics of chemically reacting multi-temperature fluid mixtures
- NeRF-Inspired Neural Fields for 3D Super-resolution of Reacting-Flows
- A conservative coupling method of sharp-interface and multi-species model for compressible reacting gas-liquid flows with phase change
BibTeX
@article{gong2026microhydration,
title = {{Microhydration Affects the Competing Product Channels of Oxygen Anion Radical Reacting With Methyl Iodide in Gas Phase}},
author = {Xulin Gong and Xiangyu Wu and Jing Xie},
journal = {ChemistryEurope},
year = {2026},
month = oct,
doi = {10.1002/ceur.70366},
url = {https://doi.org/10.1002/ceur.70366},
note = {CC BY},
}
RIS
TY - JOUR
TI - Microhydration Affects the Competing Product Channels of Oxygen Anion Radical Reacting With Methyl Iodide in Gas Phase
AU - Xulin Gong
AU - Xiangyu Wu
AU - Jing Xie
PY - 2026
DA - 2026/10/26
JO - ChemistryEurope
DO - 10.1002/ceur.70366
UR - https://doi.org/10.1002/ceur.70366
AB - Oxygen anion O− is an important radical in atmospheric, combustion, and biological chemistry. How solvation affects its reaction with haloalkane remains elusive. Here, we report a quantum chemistry calculation on the potential energy profiles of microhydrated O−(H2O)n = 0–3 anions and methyl iodide in the gas phase. The reactive nature of O− leads to multiple product channels, including the halogen abstraction (XA), SN2, proton transfer (PT), hydrogen atom transfer (HAT) pathways, and three post‐HAT pathways, namely the oxygen insertion (OxIn), HAT&PT, and HAT&XA pathways. Higher hydration levels increase both barriers and reaction enthalpies across pathways, but the differential shifts reorder the barrier heights. The OxIn pathway leading to CH2OH + I− is predicted to be the dominant product channel. This is in sharp contrast to conventional closed‐shell ion reactions where the SN2 pathway prevails. Adding water molecules to O− leads to two exothermic SN2 products, CH3O and CH3OH + I−. Remarkably, the formed CH3O, CH2OH, and CH3OH species, with or without water molecules and I− ions, can convert to each other via proton and hydrogen atom transfer. This work elucidates how individual solvent molecules affect the competing radical ion–molecule pathways, offering mechanistic insights into radical‐induced C─H bond activation in hydrocarbons.
SN - 2751-4765
ER -