Kinetic Data and Quantum Chemical Calculation Studies on the Stepwise vs. Concerted Pathways for Reaction of Chlorosulfonyl Isocyanate Reactions with Monofluoroalkenes
DIRECTORATE OF ROCKET PROPULSION EDWARDS AFB CA
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Chlorosulfonyl isocyanate CSI is known to react with hydrocarbon alkenes by a stepwise pathway. Kinetic studies and quantum chemical calculations show that CSI reacts by a concerted process with monofluoroalkenes that have a calculated vertical ionization potential IP value 8.9 eV. Monofluoroalkenes however, with IP values 8.5 eV react with CSI by a stepwise process similar to hydrocarbon alkenes. Kinetic data and quantum chemical calculations also support a pre-equilibrium complex on the reaction pathway just before the stepwise or concerted kinetic transition states. The synthetic utility of CSI reactions with unreactive hydrocarbon and monofluoroalkenes is enhanced by running the reactions at a lower temperature where the pre-equilibrium is shifted toward the complex.
- Organic Chemistry
- Physical Chemistry
- Atomic and Molecular Physics and Spectroscopy
- Quantum Theory and Relativity