Is there hydrogen bonding for gas phase SN2 pre-reaction complexes?

Jing Xie; Jiaxu Zhang; William L. Hase

doi:10.1016/j.ijms.2014.04.002

Is there hydrogen bonding for gas phase S_N2 pre-reaction complexes?

Jing Xie, Jiaxu Zhang, William L. Hase

Chemistry and Biochemistry

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

34 Scopus citations

Abstract

Abstract For some gas-phase X^- + CH₃Y → XCH₃ + Y^- S_N2 nucleophilic substitution reactions a pre-reaction complex is formed in which the attacking anion binds to a H-atom to form X^-⋯HCH₂Y. In this work properties of this complex are investigated, for the OH^- + CH₃I and F^- + CH₃I reactions, to determine whether the HO^-⋯HCH₂I and F^-⋯HCH₂I complexes should be considered hydrogen-bonded complexes. Properties considered for these complexes are their structures, vibrational frequencies, well depths, and partial atomic charges. Also considered is the role of the HO^-⋯HCH₂I complex in proton transfer for both the proton transfer and S_N2 reaction pathways. The results of these analyses indicate that these X^-⋯HCH₂Y complexes are hydrogen bonding complexes.

Original language	English
Article number	15151
Pages (from-to)	14-19
Number of pages	6
Journal	International Journal of Mass Spectrometry
Volume	378
DOIs	https://doi.org/10.1016/j.ijms.2014.04.002
State	Published - Feb 15 2015

Keywords

Hydrogen bond
Mulliken charge
Pre-reaction complex
Proton-donor

Access to Document

10.1016/j.ijms.2014.04.002

Cite this

@article{13442c8567bb449db6e3f330dd40913b,

title = "Is there hydrogen bonding for gas phase SN2 pre-reaction complexes?",

abstract = "Abstract For some gas-phase X- + CH3Y → XCH3 + Y- SN2 nucleophilic substitution reactions a pre-reaction complex is formed in which the attacking anion binds to a H-atom to form X-⋯HCH2Y. In this work properties of this complex are investigated, for the OH- + CH3I and F- + CH3I reactions, to determine whether the HO-⋯HCH2I and F-⋯HCH2I complexes should be considered hydrogen-bonded complexes. Properties considered for these complexes are their structures, vibrational frequencies, well depths, and partial atomic charges. Also considered is the role of the HO-⋯HCH2I complex in proton transfer for both the proton transfer and SN2 reaction pathways. The results of these analyses indicate that these X-⋯HCH2Y complexes are hydrogen bonding complexes.",

keywords = "Hydrogen bond, Mulliken charge, Pre-reaction complex, Proton-donor",

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

year = "2015",

month = feb,

day = "15",

doi = "10.1016/j.ijms.2014.04.002",

language = "English",

volume = "378",

pages = "14--19",