Effect of substituents on the thermal decomposition of diazirines: experimental and computational studies.
The thermal decomposition of phenylchlorodiazirine (1), phenyl-n-butyldiazirine (2), and 2-adamantane-2,3'-[3H]diazirine (3) has been studied in solution in the presence of C(60). The C(60) probe technique indicates that in the decomposition diazirine 1 yielded exclusively phenylchlorocarbene, diazirine 2 yielded mainly a diazo intermediate, and diazirine 3 yielded a mixture of carbene and diazo compound. In the case of diazirine 2, 13% of (E)-1-phenyl-1-pentene resulted from the direct thermal rearrangement of diazirine without the participation of a carbene. As well, the thermal decomposition of these diazirines has been studied theoretically with ab initio and density functional methods. The experimental results are broadly in agreement with the theoretical predictions. The calculations further indicate that the rebound reaction between carbene and molecular nitrogen leading to the formation of a diazo intermediate is an important reaction in the gas-phase decomposition of diazirine.