Asset Details
Do you wish to reserve the book?
Unexpected steric hindrance failure in the gas phase F− + (CH3)3CI SN2 reaction
Hey, we have placed the reservation for you!
By the way, why not check out events that you can attend while you pick your title.
Oops! Something went wrong.
Looks like we were not able to place the reservation. Kindly try again later.
Are you sure you want to remove the book from the shelf?
Unexpected steric hindrance failure in the gas phase F− + (CH3)3CI SN2 reaction
Do you wish to request the book?
Unexpected steric hindrance failure in the gas phase F− + (CH3)3CI SN2 reaction
Please be aware that the book you have requested cannot be checked out. If you would like to checkout this book, you can reserve another copy
We have requested the book for you!
Your request is successful and it will be processed during the Library working hours. Please check the status of your request in My Requests.
Oops! Something went wrong.
Looks like we were not able to place your request. Kindly try again later.
Journal Article
Unexpected steric hindrance failure in the gas phase F− + (CH3)3CI SN2 reaction
2022
Overview
Base-induced elimination (E2) and bimolecular nucleophilic substitution (S
N
2) reactions are of significant importance in physical organic chemistry. The textbook example of the retardation of S
N
2 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 S
N
2 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
−
+ (CH
3
)
3
CI 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 S
N
2 when the E2 pathway is completely blocked, indicating the reaction that intends to proceed via E2 transits to S
N
2 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 S
N
2 for the F
−
+ (CH
3
)
3
CI reaction. Our study provides new insight into the dynamical origin that determines the intrinsic reactivity in gas-phase organic chemistry.
Base-induced elimination (E2) and bimolecular nucleophilic substitution (SN2) are of significant importance in physical organic chemistry. Here, the authors show that the competing factor of E2 as opposed to steric hindrance determines the low reactivity of SN2 in the F
−
+ (CH
3
)
3
CI reaction.
Publisher
Nature Publishing Group UK,Nature Publishing Group,Nature Portfolio
