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

Journal Article · Wed Dec 16 00:00:00 EST 1981 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00415a042· OSTI ID:5548103

Kurz, J L; Lee, J; Rhodes, S

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)

• Research Organization: Washington Univ., St. Louis, MO
• OSTI ID: 5548103
• Journal Information: J. Am. Chem. Soc.; (United States), Vol. 103:25
• Country of Publication: United States
• Language: English

Related Subjects

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)