Addition of difluoroamino radicals to double and triple bonds

15 ADDITION OF DIFLUOROAMINO RADICALS TO DOUBLE AND TRIPLE BONDS 

The difluoroamino radical is the only radical with the free electron situated on the nitrogen atom other than atomic nitrogen for which kinetic data for olefin addition have been accumulated. The only studies are those of Trotman-Dickenson and his co-workers [156—158]. 

Relative reactivity at 373 K of various olefins towards difluoroamino radicals [156, 158] 

N2F4 dissociates readily into difluoroamino radicals, and these add to olefinic bonds slowly and reversibly 

The absolute rate studies are summarized in Table 45. From these data relative rates can, of course, be calculated, and these are presented in Table 46. These relative rates indicate that the difluoroamino radical is rather electrophilic, with considerable discriminatory powers in reaction with olefins. The reactivity of vinyl fluoride seems much too low, but the investigators acknowledge experimental difficulty in measuring the rate with this compound. 

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