ChemInform Abstract: Ab initio Molecular Orbital Calculations of Electronic Effects on the Kinetics of Cyclopropylcarbinyl Radical Ring Openings.

✍ Scribed by F. N. MARTINEZ; H. B. SCHLEGEL; M. NEWCOMB

• Publisher: John Wiley and Sons
• Year: 2010
• Weight: 26 KB
• Volume: 29
• Category: Article
• ISSN: 0931-7597
• DOI: 10.1002/chin.199835034

✦ Synopsis

Ab initio Molecular Orbital Calculations of Electronic Effects on the Kinetics of Cyclopropylcarbinyl Radical Ring Openings.

-The heats of reaction and barriers for ring opening of cyclopropylcarbinyl radicals with a vinyl or methoxy substituent at each possible position or a methyl substituent at the radical center are computed. Comparison of the computational results with experimental thermochemical and kinetic data shows good agreement in an absolute sense. Vinyl substituents on the ring reduce much more the barrier for ring opening than methoxy substituents. A methyl substituent at the radical center decreases slightly the barrier whereas a vinyl or methoxy substituent at the radical center raises the barrier for ring opening.