N-arylnitreniurn ions

Abstract

Publisher Summary Nitrenium ions are divalent nitrogen-centered cations that are isoelectronic with carbenes. They exhibit singlet and triplet electronic states; triplet state being more stable. The singlet state of N-arylnitrenium ions is stabilized by interaction of the π -system of the aryl ring with the empty p-orbital of the sp 2 hybridized nitrogen. Most of the N-arylnitrenium ions are ground-state singlets. This chapter focuses on the developments in the field of N-arylnitrenium ion chemistry and discusses N-arylnitrenium ions, simply as nitrenium ions unless in conditions where specific comparisons are made to other types of nitrenium ions. It describes the chemistry of Nitrenium ions prior to and since the year 1990 and illustrates reactions with N − 3 and solvent; reactions with carbon, nitrogen, and sulfur nucleophiles; and direct observation of nitrenium ions, including acid–base chemistry and singlet–triplet chemistry.