Microsolvated F-(H2O) + CH3I SN2 Reaction Dynamics. Insight into the Suppressed Formation of Solvated Products

Jiaxu Zhang; Li Yang; Jing Xie; William L. Hase

doi:10.1021/acs.jpclett.5b02780

Microsolvated F^-(H₂O) + CH₃I S_N2 Reaction Dynamics. Insight into the Suppressed Formation of Solvated Products

Jiaxu Zhang, Li Yang, Jing Xie, William L. Hase

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

32 Scopus citations

Abstract

Microsolvation offers a bottom-up approach to investigate details of how solute-solvent interactions affect chemical reaction dynamics. The dynamics of the microsolvated S_N2 reaction F^-(H₂O) + CH₃I are uncovered in detail by using direct chemical dynamics simulations. Direct rebound and stripping and indirect atomic-level mechanisms are observed. The indirect events comprise 70% of the solvated reaction and occur predominantly via a hydrogen-bonded F^-(H₂O)···HCH₂I prereaction complex. The reaction dynamics show propensity for the direct three-body dissociation channel F^-(H₂O) + CH₃I CH₃F + I^- + H₂O after passing the reaction's dynamical bottleneck. The water molecule leaves the reactive system before traversing the postreaction region of the PES, where water transfer toward the product species occurs. This provides an insight into the very interesting finding of strongly suppressed formation of energetically favored solvated products for almost all S_N2 reactions under microsolvation.

Original language	English (US)
Pages (from-to)	660-665
Number of pages	6
Journal	Journal of Physical Chemistry Letters
Volume	7
Issue number	4
DOIs	https://doi.org/10.1021/acs.jpclett.5b02780
State	Published - Feb 18 2016

Bibliographical note

Funding Information:
This work is supported by the National Natural Science Foundation of China (Grants 21573052, 21403047, 51536002), the Fundamental Research Funds for the Central Universities, China (AUGA5710012114, 5710012014), the SRF for ROCS, SEM, China, and the Open Project of Beijing National Laboratory for Molecular Sciences (Grant 20140103). The research reported here by W.L.H. is supported by the Robert A. Welch Foundation under Grant No. D-0005. Support is also provided by the High Performance Computing Center (HPCC) at Texas Tech University, under the direction of Philip W. Smith.

Publisher Copyright:
© 2016 American Chemical Society.

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10.1021/acs.jpclett.5b02780

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title = "Microsolvated F-(H2O) + CH3I SN2 Reaction Dynamics. Insight into the Suppressed Formation of Solvated Products",

abstract = "Microsolvation offers a bottom-up approach to investigate details of how solute-solvent interactions affect chemical reaction dynamics. The dynamics of the microsolvated SN2 reaction F-(H2O) + CH3I are uncovered in detail by using direct chemical dynamics simulations. Direct rebound and stripping and indirect atomic-level mechanisms are observed. The indirect events comprise 70% of the solvated reaction and occur predominantly via a hydrogen-bonded F-(H2O)···HCH2I prereaction complex. The reaction dynamics show propensity for the direct three-body dissociation channel F-(H2O) + CH3I CH3F + I- + H2O after passing the reaction's dynamical bottleneck. The water molecule leaves the reactive system before traversing the postreaction region of the PES, where water transfer toward the product species occurs. This provides an insight into the very interesting finding of strongly suppressed formation of energetically favored solvated products for almost all SN2 reactions under microsolvation.",

author = "Jiaxu Zhang and Li Yang and Jing Xie and Hase, {William L.}",

note = "Funding Information: This work is supported by the National Natural Science Foundation of China (Grants 21573052, 21403047, 51536002), the Fundamental Research Funds for the Central Universities, China (AUGA5710012114, 5710012014), the SRF for ROCS, SEM, China, and the Open Project of Beijing National Laboratory for Molecular Sciences (Grant 20140103). The research reported here by W.L.H. is supported by the Robert A. Welch Foundation under Grant No. D-0005. Support is also provided by the High Performance Computing Center (HPCC) at Texas Tech University, under the direction of Philip W. Smith. Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

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