Effects of solvent-solute interactions on the stereochemical course in high energy chlorine-38-for chlorine substitution in meso- and rac-1,2-dichloro-1,2-difluoroethane in solution

Journal Article · Thu May 04 04:00:00 EDT 1978 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100498a002· OSTI ID:7092124

Acciani, T R ^[1]; Su, Y Y; Ache, H J; Rack, E P

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1. Virginia Polytechnic Inst. and State Univ., Blacksburg

The stereochemistry of the chlorine-38-for-chlorine substitution was studied in diastereomeric 1,2-dichloro-1,2-difluoroethanes in solutions. The experimental results are very similar to those previously observed in meso- and d,l-2,4-dichloropentane solutions which by analogy suggest that the stereochemical course of the substitution process is in the present system also predominantly and directly controlled by the properties of the solvent molecules, most likely by the factors which govern the magnitude of intermolecular interaction between reactants and solvents. It appears that strong intermolecular interaction favors substitution via retention of configuration, whereas in solvents having a low dielectric constant the retention/inversion ratio decreases. These results seem further to suggest that if the reaction occurs via the previously postulated caged complex or excited intermediate that the primary attack by the energetic /sup 38/Cl proceeds via both front and backside replacement.

• OSTI ID: 7092124
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 82:9; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400203 -- Isotope Exchange & Isotope Separation-- (-1987)
400701* -- Radiochemistry & Nuclear Chemistry-- Hot-Atom Chemistry
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
BROMINE
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
CHLORINE
CHLORINE 38
CHLORINE ISOTOPES
CHROMATOGRAPHY
ELEMENTS
ENERGY LEVELS
EXCHANGE INTERACTIONS
EXCITED STATES
GAS CHROMATOGRAPHY
HALOGENATED ALIPHATIC HYDROCARBONS
HALOGENS
HOT ATOM CHEMISTRY
INTERACTIONS
IODINE
IRRADIATION
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
ISOTOPIC EXCHANGE
KINETICS
LABELLING
LIGHT NUCLEI
MAGNETIC RESONANCE
MINUTES LIVING RADIOISOTOPES
NONMETALS
NUCLEAR MAGNETIC RESONANCE
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
RADIOCHEMISTRY
RADIOISOTOPES
REACTION KINETICS
RESONANCE
SAMPLE PREPARATION
SECONDS LIVING RADIOISOTOPES
SEPARATION PROCESSES
SOLVENT PROPERTIES
STEREOCHEMISTRY
STRUCTURAL CHEMICAL ANALYSIS