Addition of nitrogen atoms to double and triple bonds

10 ADDITION OF NITROGEN ATOMS TO DOUBLE AND TRIPLE BONDS 

The relative reactivities of a series of olefins towards nitrogen atoms shows a close parallel with the relative reactivity of the same olefins with 

Certainly the very substantial spread of relative reactivities that was observed for the reaction of much the same olefins with oxygen, sulphur and bromine atoms, discussed in an earlier section, is not observed with nitrogen atoms. 

The kinetic data for reaction of nitrogen atoms with ethylene are summarized in Table 37, where much of the work is by Herron and co-workers. The very much lower rate coefficients for reaction of nitrogen atoms as compared with the analogous hydrogen atom addition should be noted (roughly a factor of ten). 

The best value of log k is probably somewhere near 7.0, but there is no certainty about it. Herron et al. have shown that the purity of the nitrogen atoms is crucial. According to the authors, values for log k given in refs. 127 and 128 are the consequence of different purities of nitrogen. But, it is wise to recall that since the rates have been measured in terms of disappearance of nitrogen atoms or appearance of HCN, rather than appearance of the primary adduct, whatever that may be, then the data are inherently somewhat suspect. 

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