Kinetic Data and Quantum Chemical Calculation Studies on the Stepwise vs. Concerted Pathways for Reaction of Chlorosulfonyl Isocyanate Reactions with Monofluoroalkenes
Abstract
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.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jan 17, 2013
- Accession Number
- ADA591660
Entities
People
- Dale F. Shellhamer
- Danielle E. Shipowick
- Jacob C. Milligan
- Jerry A. Boatz
- Lincoln B. Smith
Organizations
- Air Force Research Laboratory