Deuterium and oxygen-18 isotope effects on nucleophilic displacement by water
Kinetic deuterium isotope effects (k/sub H/sub 2/O//k/sub D/sub 2/O/) have been measured for nucleophilic attack by water at primary alkyl carbon (S-methylthiophenium ion (MeTh+), methyl trifluoromethane-sulfonate (MeOTf), methyl and ethyl perchlorate (MeOClO/sub 3/, EtOClO/sub 3/)) in aprotic solvents (acetonitrile (MeCN) and tetrahydrothiophene-1, 1-dioxide (TMSO/sub 2/; solfolane)) and L/sub 2/O. In L/sub 2/O solvent k/sub H/sub 2/O//k/sub D/sub 2/O/ is significantly greater than unity while it is reduced to near unity in aprotic solvents. The oxygen-18 isotope effect has also been observed to be 1.002 +- 0.004 for the reaction of MeTh/sup +/ with dilute H/sub 2/O in TMSO/sub 2/ at 35/sup 0/C. For the reaction of MeTh/sup +/ and MeOClO/sub 3/ in aprotic solvents the chemical reaction kinetics are discussed.
- Research Organization:
- Washington Univ., Seattle (USA)
- OSTI ID:
- 5583035
- Resource Relation:
- Other Information: Thesis (Ph. D.)
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
DEUTERIUM
ISOTOPE EFFECTS
OXYGEN 18
ACETONITRILE
AROMATICS
CATIONS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPARATIVE EVALUATIONS
DEUTERIUM COMPOUNDS
ESTERS
EXPERIMENTAL DATA
FLUORINATED ALIPHATIC HYDROCARBONS
HEAVY WATER
HETEROCYCLIC COMPOUNDS
MEDIUM TEMPERATURE
ORGANIC SULFUR COMPOUNDS
PERCHLORATES
SULFONIC ACID ESTERS
SULFOXIDES
TEMPERATURE DEPENDENCE
WATER
CHARGED PARTICLES
CHLORINE COMPOUNDS
DATA
EVEN-EVEN NUCLEI
HALOGEN COMPOUNDS
HALOGENATED ALIPHATIC HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
IONS
ISOTOPES
KINETICS
LIGHT NUCLEI
NITRILES
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
OXYGEN ISOTOPES
REACTION KINETICS
STABLE ISOTOPES
400302* - Organic Chemistry- Isotope Effects- (-1987)