Solvent isotope effect on the rate of methoxyl exchange between methyl borate and methanol
Journal Article
·
· J. Am. Chem. Soc.; (United States)
NMR studies of methyl borate in methanol solution indicate fast methoxyl exchange with a large deuterium solvent isotope effect: k/sub CH/sub 3/OH//k/sub CH/sub 3/OD/ = 11.0 at 25/sup 0/C. The temperature dependence of the first-order rate constants (s/sup -1/) is given by k/sub CH/sub 3/OH/ = 5.7 x 10/sup 3/ e/sup -2360/RT/ and k/sub CH/sub 3/OD/ = 9.1 x 10/sup 3/ e/sup -4060/RT/. These constants refer to a pH-independent phase of the exchange. Catalysis by lyonium and lyate ions occurs with approximate rate constants (M/sup -1/ s/sup -1/) k/sub CH/sub 3/OH/sub 2//sup +// = 1.4 x 10/sup 5/, k/sub CH/sub 3/OD/sub 2//sup +// = 1.0 x 10/sup 5/, and k/sub CH/sub 3/O/sup -// = 7 x 10/sup 10/. 4 figs.
- Research Organization:
- Univ. of Virginia, Charlottesville
- OSTI ID:
- 6374608
- Journal Information:
- J. Am. Chem. Soc.; (United States), Vol. 100:22
- Country of Publication:
- United States
- Language:
- English
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OSTI ID:6374608
Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BORON OXIDES
CHEMICAL REACTIONS
DEUTERIUM
ISOTOPE EFFECTS
METHANOL
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
DEUTERIUM COMPOUNDS
IONS
MEDIUM TEMPERATURE
NUCLEAR MAGNETIC RESONANCE
ORGANIC SOLVENTS
TEMPERATURE DEPENDENCE
ALCOHOLS
BORON COMPOUNDS
CHALCOGENIDES
CHARGED PARTICLES
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
HYDROXY COMPOUNDS
ISOTOPES
KINETICS
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
REACTION KINETICS
RESONANCE
SOLVENTS
STABLE ISOTOPES
400302* - Organic Chemistry- Isotope Effects- (-1987)
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BORON OXIDES
CHEMICAL REACTIONS
DEUTERIUM
ISOTOPE EFFECTS
METHANOL
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
DEUTERIUM COMPOUNDS
IONS
MEDIUM TEMPERATURE
NUCLEAR MAGNETIC RESONANCE
ORGANIC SOLVENTS
TEMPERATURE DEPENDENCE
ALCOHOLS
BORON COMPOUNDS
CHALCOGENIDES
CHARGED PARTICLES
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
HYDROXY COMPOUNDS
ISOTOPES
KINETICS
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
REACTION KINETICS
RESONANCE
SOLVENTS
STABLE ISOTOPES
400302* - Organic Chemistry- Isotope Effects- (-1987)