Ab initio computational insight into the ion-pair SN2 reaction of lithium isothiocyanate and methyl fluoride in the gas phase and in acetone solution

Yi Ren; Ming Li; Ning-Bew Wong; San-Yan Chu

doi:10.1007/s00894-005-0016-8

Ab initio computational insight into the ion-pair S_N2 reaction of lithium isothiocyanate and methyl fluoride in the gas phase and in acetone solution

Yi Ren
, Ming Li
, Ning-Bew Wong
, San-Yan Chu

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

9 Citations (Scopus)

Abstract

The ion-pair S_N2 reaction LiNCS + CH₃F with two mechanisms, inversion and retention, was investigated at the MP2(full)/6-311+G**//HF/6-311+G** level in the gas phase and in acetone solution. All HF-optimized structures were confirmed by vibrational frequency analysis. Based on IRC analyses, eight possible reaction pathways in the title reaction are proposed. The inversion mechanism through a six-membered-ring transition-state structure is the most favorable. Methyl thiocyanate should form preferentially in the gas phase and the more stable methyl isothiocyanate will be the main product in CH₃COCH₃. The retardation of the reaction in CH₃COCH₃ solution was attributed to the differences in the solvation free energies in the separated reactants and transition structures. All of the theoretical results are consistent with the experiment. © Springer-Verlag 2005.

Original language	English
Pages (from-to)	182-189
Journal	Journal of Molecular Modeling
Volume	12
Issue number	2
DOIs	https://doi.org/10.1007/s00894-005-0016-8
Publication status	Published - Jan 2006

Bibliographical note

Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].

Funding

This work was funded by the Science Foundation of Chongqing City, PRC (Grant No.2002-7473).

Research Keywords

Ab initio
Inversion and retention mechanisms
Ion-pair SN2 reaction
Thiocyanates and isothiocyanates

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10.1007/s00894-005-0016-8

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Cite this

@article{206ca2388fd34c75b3032747ded5874b,

title = "Ab initio computational insight into the ion-pair SN2 reaction of lithium isothiocyanate and methyl fluoride in the gas phase and in acetone solution",

abstract = "The ion-pair SN2 reaction LiNCS + CH3F with two mechanisms, inversion and retention, was investigated at the MP2(full)/6-311+G**//HF/6-311+G** level in the gas phase and in acetone solution. All HF-optimized structures were confirmed by vibrational frequency analysis. Based on IRC analyses, eight possible reaction pathways in the title reaction are proposed. The inversion mechanism through a six-membered-ring transition-state structure is the most favorable. Methyl thiocyanate should form preferentially in the gas phase and the more stable methyl isothiocyanate will be the main product in CH3COCH3. The retardation of the reaction in CH3COCH3 solution was attributed to the differences in the solvation free energies in the separated reactants and transition structures. All of the theoretical results are consistent with the experiment. {\textcopyright} Springer-Verlag 2005.",

keywords = "Ab initio, Inversion and retention mechanisms, Ion-pair SN2 reaction, Thiocyanates and isothiocyanates",

author = "Yi Ren and Ming Li and Ning-Bew Wong and San-Yan Chu",

note = "Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].",

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Ab initio computational insight into the ion-pair S_N2 reaction of lithium isothiocyanate and methyl fluoride in the gas phase and in acetone solution. / Ren, Yi; Li, Ming; Wong, Ning-Bew et al.
In: Journal of Molecular Modeling, Vol. 12, No. 2, 01.2006, p. 182-189.

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

TY - JOUR

T1 - Ab initio computational insight into the ion-pair SN2 reaction of lithium isothiocyanate and methyl fluoride in the gas phase and in acetone solution

AU - Ren, Yi

AU - Li, Ming

AU - Wong, Ning-Bew

AU - Chu, San-Yan

N1 - Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].

PY - 2006/1

Y1 - 2006/1

N2 - The ion-pair SN2 reaction LiNCS + CH3F with two mechanisms, inversion and retention, was investigated at the MP2(full)/6-311+G**//HF/6-311+G** level in the gas phase and in acetone solution. All HF-optimized structures were confirmed by vibrational frequency analysis. Based on IRC analyses, eight possible reaction pathways in the title reaction are proposed. The inversion mechanism through a six-membered-ring transition-state structure is the most favorable. Methyl thiocyanate should form preferentially in the gas phase and the more stable methyl isothiocyanate will be the main product in CH3COCH3. The retardation of the reaction in CH3COCH3 solution was attributed to the differences in the solvation free energies in the separated reactants and transition structures. All of the theoretical results are consistent with the experiment. © Springer-Verlag 2005.

AB - The ion-pair SN2 reaction LiNCS + CH3F with two mechanisms, inversion and retention, was investigated at the MP2(full)/6-311+G**//HF/6-311+G** level in the gas phase and in acetone solution. All HF-optimized structures were confirmed by vibrational frequency analysis. Based on IRC analyses, eight possible reaction pathways in the title reaction are proposed. The inversion mechanism through a six-membered-ring transition-state structure is the most favorable. Methyl thiocyanate should form preferentially in the gas phase and the more stable methyl isothiocyanate will be the main product in CH3COCH3. The retardation of the reaction in CH3COCH3 solution was attributed to the differences in the solvation free energies in the separated reactants and transition structures. All of the theoretical results are consistent with the experiment. © Springer-Verlag 2005.

KW - Ab initio

KW - Inversion and retention mechanisms

KW - Ion-pair SN2 reaction

KW - Thiocyanates and isothiocyanates

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