Thermodynamics and kinetics of carbon-carbon bond formation and heterolysis through reactions of carbocations with carbanions in solution
Rate data are presented for the heterolysis of carbon-carbon bonds and their formation through coordination of resonance-stabilized carbocations and carbanions in acetonitrile solution at 25/sup 0/C. These rates were determined by NMR line broadening and by the T jump technique (in a solution containing 0.48 M supporting electrolyte). Preliminary results are given for a master equation to predict some heterolysis energies in solution as a complement to Benson's method for homolysis energies. The results provide for the first time an opportunity to compare the effects of structure variation on the kinetic and thermodynamic properties for such an ostensibly simple reaction in solution. On the basis of these results and many others which have appeared recently it may be appropriate to discard the reactivity selectivity principle as a useful principle for either prediction or interpretation. 69 references, 2 figures, 3 tables.
- Research Organization:
- Duke Univ., Durham, NC
- OSTI ID:
- 5896644
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 90:3; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Master equations for calculating heterolysis energies in solution
Related Subjects
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ACETONITRILE
ANIONS
BINDING ENERGY
CATIONS
CHARGED PARTICLES
CHEMICAL REACTIONS
DATA
ENERGY
EXPERIMENTAL DATA
FREE ENERGY
FREE ENTHALPY
INFORMATION
IONS
LINE WIDTHS
MAGNETIC RESONANCE
MEDIUM TEMPERATURE
MEETINGS
NITRILES
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHYSICAL PROPERTIES
RESONANCE
SOLVENT PROPERTIES
THERMODYNAMIC PROPERTIES