Unexpected steric hindrance failure in the gas phase F− + (CH3)3CI SN2 reaction

Xiaoxiao Lu, Chenyao Shang, Lulu Li, Rongjun Chen, Bina Fu (), Xin Xu and Dong H. Zhang ()
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Xiaoxiao Lu: Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Chenyao Shang: Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Lulu Li: Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Rongjun Chen: Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Bina Fu: Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Xin Xu: Fudan University
Dong H. Zhang: Dalian Institute of Chemical Physics, Chinese Academy of Sciences

Nature Communications, 2022, vol. 13, issue 1, 1-7

Abstract: Abstract Base-induced elimination (E2) and bimolecular nucleophilic substitution (SN2) reactions are of significant importance in physical organic chemistry. The textbook example of the retardation of SN2 reactivity by bulky alkyl substitution is widely accepted based on the static analysis of molecular structure and steric environment. However, the direct dynamical evidence of the steric hindrance of SN2 from experiment or theory remains rare. Here, we report an unprecedented full-dimensional (39-dimensional) machine learning-based potential energy surface for the 15-atom F− + (CH3)3CI reaction, facilitating the reliable and efficient reaction dynamics simulations that can reproduce well the experimental outcomes and examine associated atomic-molecular level mechanisms. Moreover, we found surprisingly high “intrinsic” reactivity of SN2 when the E2 pathway is completely blocked, indicating the reaction that intends to proceed via E2 transits to SN2 instead, due to a shared pre-reaction minimum. This finding indicates that the competing factor of E2 but not the steric hindrance determines the small reactivity of SN2 for the F− + (CH3)3CI reaction. Our study provides new insight into the dynamical origin that determines the intrinsic reactivity in gas-phase organic chemistry.

Date: 2022
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DOI: 10.1038/s41467-022-32191-6

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