Abstract
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 D0°(tBu–H) of 89.0 kcal mole−1. Activation energies at 0°K for tBu and Me radical addition to olefins are discussed; some disproportionation-recombination ratios involving tBu radical were obtained.
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