Carbon and secondary deuterium kinetic isotope effects on SN2 methyl transfer reactions

Joanna Dzierzawska; Arkadiusz Jarota; Michal Karolak; Lukasz Piotrowski; Izabela Placek; Katarzyna Swiderek; Lukasz Szatkowski; Piotr Paneth

doi:10.1002/poc.1267

Carbon and secondary deuterium kinetic isotope effects on SN2 methyl transfer reactions

Joanna Dzierzawska, Arkadiusz Jarota, Michal Karolak, Lukasz Piotrowski, Izabela Placek, Katarzyna Swiderek, Lukasz Szatkowski, Piotr Paneth

University of Missouri-St. Louis

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

Abstract

Carbon and secondary deuterium kinetic isotope effect (KIE) for three types of S N 2 methyl transfer reactions have been predicted theoretically at a DFT level in gas phase and in aqueous solution modelled by the PCM continuum solvent model. No correlation between these isotope effects and geometrical features of the corresponding transition states (TSs), force constants of the imaginary frequency or Gibbs free energies of the studied reactions has been found. These findings suggest that comparative analysis of the magnitudes of the studied KIEs should be constrained to interpretation of the TS localization on the reaction coordinate only in a series of very closely related reactions. Copyright © 2007 John Wiley & Sons, Ltd.

Original language	American English
Journal	Journal of Physical Organic Chemistry
Volume	20
DOIs	https://doi.org/10.1002/poc.1267
State	Published - Dec 2007

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Chemistry

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title = "Carbon and secondary deuterium kinetic isotope effects on SN2 methyl transfer reactions",

abstract = " Carbon and secondary deuterium kinetic isotope effect (KIE) for three types of S N 2 methyl transfer reactions have been predicted theoretically at a DFT level in gas phase and in aqueous solution modelled by the PCM continuum solvent model. No correlation between these isotope effects and geometrical features of the corresponding transition states (TSs), force constants of the imaginary frequency or Gibbs free energies of the studied reactions has been found. These findings suggest that comparative analysis of the magnitudes of the studied KIEs should be constrained to interpretation of the TS localization on the reaction coordinate only in a series of very closely related reactions. Copyright {\textcopyright} 2007 John Wiley & Sons, Ltd. ",

author = "Joanna Dzierzawska and Arkadiusz Jarota and Michal Karolak and Lukasz Piotrowski and Izabela Placek and Katarzyna Swiderek and Lukasz Szatkowski and Piotr Paneth",

year = "2007",

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doi = "10.1002/poc.1267",

language = "American English",

volume = "20",

journal = "Journal of Physical Organic Chemistry",

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TY - JOUR

T1 - Carbon and secondary deuterium kinetic isotope effects on SN2 methyl transfer reactions

AU - Dzierzawska, Joanna

AU - Jarota, Arkadiusz

AU - Karolak, Michal

AU - Piotrowski, Lukasz

AU - Placek, Izabela

AU - Swiderek, Katarzyna

AU - Szatkowski, Lukasz

AU - Paneth, Piotr

PY - 2007/12

Y1 - 2007/12

N2 - Carbon and secondary deuterium kinetic isotope effect (KIE) for three types of S N 2 methyl transfer reactions have been predicted theoretically at a DFT level in gas phase and in aqueous solution modelled by the PCM continuum solvent model. No correlation between these isotope effects and geometrical features of the corresponding transition states (TSs), force constants of the imaginary frequency or Gibbs free energies of the studied reactions has been found. These findings suggest that comparative analysis of the magnitudes of the studied KIEs should be constrained to interpretation of the TS localization on the reaction coordinate only in a series of very closely related reactions. Copyright © 2007 John Wiley & Sons, Ltd.

AB - Carbon and secondary deuterium kinetic isotope effect (KIE) for three types of S N 2 methyl transfer reactions have been predicted theoretically at a DFT level in gas phase and in aqueous solution modelled by the PCM continuum solvent model. No correlation between these isotope effects and geometrical features of the corresponding transition states (TSs), force constants of the imaginary frequency or Gibbs free energies of the studied reactions has been found. These findings suggest that comparative analysis of the magnitudes of the studied KIEs should be constrained to interpretation of the TS localization on the reaction coordinate only in a series of very closely related reactions. Copyright © 2007 John Wiley & Sons, Ltd.

UR - https://doi.org/10.1002/poc.1267

U2 - 10.1002/poc.1267

DO - 10.1002/poc.1267

M3 - Article

VL - 20

JO - Journal of Physical Organic Chemistry

JF - Journal of Physical Organic Chemistry

ER -

Carbon and secondary deuterium kinetic isotope effects on SN2 methyl transfer reactions

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