F- + CH3I → FCH3 + I- reaction dynamics. Nontraditional atomistic mechanisms and formation of a hydrogen-bonded complex

Jiaxu Zhang; Jochen Mikosch; Sebastian Trippel; Rico Otto; Matthias Weidemüller; Roland Wester; William L. Hase

doi:10.1021/jz1010658

F^- + CH₃I → FCH₃ + I^- reaction dynamics. Nontraditional atomistic mechanisms and formation of a hydrogen-bonded complex

Jiaxu Zhang, Jochen Mikosch, Sebastian Trippel, Rico Otto, Matthias Weidemüller, Roland Wester, William L. Hase

Chemistry and Biochemistry

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Abstract

Ion imaging experiments and direct chemical dynamics simulations were performed to study the atomic-level dynamics for the F^- + CH ₃I → FCH₃ + I^- S_N2 nucleophilic substitution reaction at 0.32 eV collision energy. The simulations reproduce the product energy partitionings and the velocity scattering angle distribution measured in the experiments. The simulations reveal that the substitution reaction occurs by two direct atomic-level mechanisms, that is, rebound and stripping, and an indirect mechanism. Approximately 90% of the indirect events occur via a prereaction F^--HCH₂I hydrogen-bonded complex. This mechanism may play an important role for other F^- S_N2 reactions due to the strong electronegativity of fluorine. The average product energy partitioning for the F^- + CH₃I indirect mechanism agrees with the prediction of PST, even though a FCH₃-I^- postreaction complex is not formed.

Original language	English
Pages (from-to)	2747-2752
Number of pages	6
Journal	Journal of Physical Chemistry Letters
Volume	1
Issue number	18
DOIs	https://doi.org/10.1021/jz1010658
State	Published - Sep 16 2010

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abstract = "Ion imaging experiments and direct chemical dynamics simulations were performed to study the atomic-level dynamics for the F- + CH 3I → FCH3 + I- SN2 nucleophilic substitution reaction at 0.32 eV collision energy. The simulations reproduce the product energy partitionings and the velocity scattering angle distribution measured in the experiments. The simulations reveal that the substitution reaction occurs by two direct atomic-level mechanisms, that is, rebound and stripping, and an indirect mechanism. Approximately 90% of the indirect events occur via a prereaction F--HCH2I hydrogen-bonded complex. This mechanism may play an important role for other F- SN2 reactions due to the strong electronegativity of fluorine. The average product energy partitioning for the F- + CH3I indirect mechanism agrees with the prediction of PST, even though a FCH3-I- postreaction complex is not formed.",

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AU - Zhang, Jiaxu

AU - Mikosch, Jochen

AU - Trippel, Sebastian

AU - Otto, Rico

AU - Weidemüller, Matthias

AU - Wester, Roland

AU - Hase, William L.

PY - 2010/9/16

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N2 - Ion imaging experiments and direct chemical dynamics simulations were performed to study the atomic-level dynamics for the F- + CH 3I → FCH3 + I- SN2 nucleophilic substitution reaction at 0.32 eV collision energy. The simulations reproduce the product energy partitionings and the velocity scattering angle distribution measured in the experiments. The simulations reveal that the substitution reaction occurs by two direct atomic-level mechanisms, that is, rebound and stripping, and an indirect mechanism. Approximately 90% of the indirect events occur via a prereaction F--HCH2I hydrogen-bonded complex. This mechanism may play an important role for other F- SN2 reactions due to the strong electronegativity of fluorine. The average product energy partitioning for the F- + CH3I indirect mechanism agrees with the prediction of PST, even though a FCH3-I- postreaction complex is not formed.

AB - Ion imaging experiments and direct chemical dynamics simulations were performed to study the atomic-level dynamics for the F- + CH 3I → FCH3 + I- SN2 nucleophilic substitution reaction at 0.32 eV collision energy. The simulations reproduce the product energy partitionings and the velocity scattering angle distribution measured in the experiments. The simulations reveal that the substitution reaction occurs by two direct atomic-level mechanisms, that is, rebound and stripping, and an indirect mechanism. Approximately 90% of the indirect events occur via a prereaction F--HCH2I hydrogen-bonded complex. This mechanism may play an important role for other F- SN2 reactions due to the strong electronegativity of fluorine. The average product energy partitioning for the F- + CH3I indirect mechanism agrees with the prediction of PST, even though a FCH3-I- postreaction complex is not formed.

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F^- + CH₃I → FCH₃ + I^- reaction dynamics. Nontraditional atomistic mechanisms and formation of a hydrogen-bonded complex

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