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Title: Deuterium isotope effects on methyl transfer to alcohols. Possible asynchronous solvent repolarization and internal structural changes

Abstract

Alkyl substitution on nucleophilic oxygen causes large changes in the H/sub 2/O/D/sub 2/O kinetic isotope effect (KIE) on methyl transfers to water: ROL + CH/sub 3/X..-->.. RLO/sup +/ CH/sub 3/ + X/sup -/ with L=H,D; R=L. For both Meth/sup +/ and MeOClO/sub 3/, KIE for CH/sub 3/OL is greater than KIE for L/sub 2/O. When the methyl transfer is to L/sub 2/O, the small, strongly hydrogen-bonding L/sub 2/O/sup +/ moiety in the product will be very tightly solvated, and such tight solvation implies a strong coupling force between solvent polarization and internal charge distribution. (MWF)

Authors:
; ;
Publication Date:
Research Org.:
Washington Univ., St. Louis, MO
OSTI Identifier:
5548103
Resource Type:
Journal Article
Journal Name:
J. Am. Chem. Soc.; (United States)
Additional Journal Information:
Journal Volume: 103:25
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BUTANOLS; CHEMICAL REACTIONS; DEUTERIUM; ISOTOPE EFFECTS; METHANOL; EXPERIMENTAL DATA; KINETICS; MOLECULAR STRUCTURE; POLARIZATION; SOLVENTS; WATER; ALCOHOLS; DATA; HYDROGEN COMPOUNDS; HYDROGEN ISOTOPES; HYDROXY COMPOUNDS; INFORMATION; ISOTOPES; LIGHT NUCLEI; NUCLEI; NUMERICAL DATA; ODD-ODD NUCLEI; ORGANIC COMPOUNDS; OXYGEN COMPOUNDS; STABLE ISOTOPES; 400302* - Organic Chemistry- Isotope Effects- (-1987)

Citation Formats

Kurz, J L, Lee, J, and Rhodes, S. Deuterium isotope effects on methyl transfer to alcohols. Possible asynchronous solvent repolarization and internal structural changes. United States: N. p., 1981. Web. doi:10.1021/ja00415a042.
Kurz, J L, Lee, J, & Rhodes, S. Deuterium isotope effects on methyl transfer to alcohols. Possible asynchronous solvent repolarization and internal structural changes. United States. https://doi.org/10.1021/ja00415a042
Kurz, J L, Lee, J, and Rhodes, S. 1981. "Deuterium isotope effects on methyl transfer to alcohols. Possible asynchronous solvent repolarization and internal structural changes". United States. https://doi.org/10.1021/ja00415a042.
@article{osti_5548103,
title = {Deuterium isotope effects on methyl transfer to alcohols. Possible asynchronous solvent repolarization and internal structural changes},
author = {Kurz, J L and Lee, J and Rhodes, S},
abstractNote = {Alkyl substitution on nucleophilic oxygen causes large changes in the H/sub 2/O/D/sub 2/O kinetic isotope effect (KIE) on methyl transfers to water: ROL + CH/sub 3/X..-->.. RLO/sup +/ CH/sub 3/ + X/sup -/ with L=H,D; R=L. For both Meth/sup +/ and MeOClO/sub 3/, KIE for CH/sub 3/OL is greater than KIE for L/sub 2/O. When the methyl transfer is to L/sub 2/O, the small, strongly hydrogen-bonding L/sub 2/O/sup +/ moiety in the product will be very tightly solvated, and such tight solvation implies a strong coupling force between solvent polarization and internal charge distribution. (MWF)},
doi = {10.1021/ja00415a042},
url = {https://www.osti.gov/biblio/5548103}, journal = {J. Am. Chem. Soc.; (United States)},
number = ,
volume = 103:25,
place = {United States},
year = {Wed Dec 16 00:00:00 EST 1981},
month = {Wed Dec 16 00:00:00 EST 1981}
}