Mass spectrometry studies of nitrene anions

Abstract

Nitrene anions are a class of reactive intermediates that provide a means for studying the corresponding neutral molecules via electron photodetachment spectroscopy and photoelectron spectroscopy. The added electron makes it possible for protected nitrene anions to be manipulated by external electric and magnetic fields of a mass spectrometer. Nitrene anions also display their own unique reactivities as reagents, which have been investigated using ion/molecule reactions. Mass spectrometry of negative ions has thereby provided information on the electronic states, reactivities, and thermochemical properties of nitrene intermediates. This review also includes a discussion of condensed‐phase nitrene anions.

Gas‐phase F‐atom migration reaction of deprotonated N‐fluoroarenesulfonamides

“…Such F‐atom rearrangement from INTI p ‐C 6 H 4 NFSO 2 − (−23.8 kcal/mol) to INT2 p ‐CN‐C 6 H 4 N − SO 2 F (−74.5 kcal/mol) was exothermic. Finally, INT2 p ‐CN‐C 6 H 4 N − SO 2 F dissociated to SO 2 F − at m/z 83 due to the loss of a neutral nitrene p ‐CN‐C 6 H 4 N. However, the calculation results showed that the energy of the triplet‐state nitrene p ‐CN‐C 6 H 4 N is 42.2 kcal/mol less than that of the singlet‐state nitrene p ‐CN‐C 6 H 4 N, indicating that the formation of the triplet‐state nitrene p ‐CN‐C 6 H 4 N is more energetically favorable than that of the singlet‐state nitrene p ‐CN‐C 6 H 4 N 25,26 . Overall, the fragmentation of [ 2 –H] − ( p ‐CN‐C 6 H 4 SO 2 NF − ) to yield the final product ion at m/z 83 and a triplet‐state nitrene p ‐CN‐C 6 H 4 N (−14.7 kcal/mol) was exothermic.…”