Dissociative stereoisomerization of persulfuranes via 10-S-5 persulfonium salts. Geometrical isomers of octahedral 12-S-6 species
Journal Article
·
· J. Am. Chem. Soc.; (United States)
The reaction of bromine trifluoride with sulfurane gives rise to the first reported isolation of geometrical isomers of 12-S-6 sulfur, the trans- and cis-difluorodialkoxydiarylpersulfuranes. The cis isomer is 1.6 +/- 0.1 kcal/mol more favored in free energy than the all-trans isomer in methylene chloride solution at 25/sup 0/C. Calorimetry showed trans-to-cis isomerization to be exothermic by 2.0 +/- 0.5 kcal/mol. The rapid, acid-catalyzed isomerization of trans isomer to give cis isomer occurs by a dissociative mechanism through a pentacoordinate cationic sulfur intermediate, a 10-S-5 persulfonium ion, which was isolated at its hexafluorophosphate salt. A lower limit for the activation barrier of the unobserved nondissociative isomerization of trans to cis is 50 kcal/mol in quinoline solution. Polarization and other effects on the relative bond lengths and energies of the isomers are discussed. The results of complete X-ray structure determinations for trans and cis are described together with a PMO argument rationalizing the observed order of bond lengths.
- Research Organization:
- Univ. of Illinois, Urbana
- OSTI ID:
- 6739502
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 104:6; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
BROMINE COMPOUNDS
BROMINE FLUORIDES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CHEMICAL SHIFT
COORDINATES
DATA
DISSOCIATION
EXPERIMENTAL DATA
FLUORIDES
FLUORINE COMPOUNDS
FURANS
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
INFORMATION
ISOMERIZATION
ISOMERS
MEDIUM TEMPERATURE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PARAMETRIC ANALYSIS
REAGENTS
STABILITY
STOICHIOMETRY
SULFUR COMPOUNDS
SULFUR FLUORIDES
SYNTHESIS
400201 -- Chemical & Physicochemical Properties
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
BROMINE COMPOUNDS
BROMINE FLUORIDES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CHEMICAL SHIFT
COORDINATES
DATA
DISSOCIATION
EXPERIMENTAL DATA
FLUORIDES
FLUORINE COMPOUNDS
FURANS
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
INFORMATION
ISOMERIZATION
ISOMERS
MEDIUM TEMPERATURE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PARAMETRIC ANALYSIS
REAGENTS
STABILITY
STOICHIOMETRY
SULFUR COMPOUNDS
SULFUR FLUORIDES
SYNTHESIS