Competitive Unimolecular Decomposition of Alkyl Radicals. Tertiary Butyl Rupture

摘要

The competitive unimolecular decomposition of vibrationally excited 3,4,4-trimethylpentyl-2 radical was investigated. Relative and absolute rate of decomposition by tert-butyl (tBu) and methyl (Me) radical rupture were measured. Results were interpreted in terms of the Rice-Ramsperger-Kassel-Marcus (RRKM) unimolecular rate theory and lead to a value for the dissociation energy of (tBu-H) as 89.0 kcal/mole. Activation energies at 0K for tBu and Me radical addition to olefins are discussed; some disproportionation-recombination ratios involving tBu radical were obtained. (Author)