Free radical addition to olefins. Part 25.-Addition of perfluoro-t-butyl radicals to fluoro-olefins

Nonafluoro-2-iodo-2-methylpropane (perfluoro-t-butyl iodide) has been photolysed in the presence of ethylene and four fluoroethylenes. The reactions have been studied over a range of temperatures and relative Arrhenius parameters have been obtained for the addition of perfluoro-t-butyl radicals to each different site in the fluoro-olefins (E) (CF3)3C·+ E k2→ (CF3)3CĖ. olefin k 2/k2e(437 K) E2-E2e A 2/A2e (sitě) (per active site) /kcal mol -1 (per active site) ČH2=CHF 0.48 0.98 1.48 ČH2=CF2 0.33 1.11 1.20 ČHF=CH2 0.0025 4.31 0.37 ČHF=CF2 0.013 3.03 0.41 ČF 2=CHF 0.00027 5.47 0.15 ČF2=CF2 0.0008 4.06 0.09 (Subscript e refers to ethylene).