Multimodal Reactivity of N-H Bonds in Triazanes and Isolation of a Triazinyl Radical

The employment of nitrogen Lewis acids based on nitrenium cations has been increasingly featured in the fields of main group chemistry and catalysis. A formally reduced form of nitrenium D─cyclic triazanes E─are intriguing chemical compounds, the chemistry of which is completely unexplored. In this work, we reveal that N-H-triazanes exhibit unusual N-H bond properties; namely, they can serve as protons, hydrides, or hydrogen atom donors. This unique multimodal reactivity provides an N-cation, N-anion, or N-radical from the same species. It allowed us to isolate, for the first time, a stable naphto[1,2,3]triazinyl radical, which was fully characterized both computationally and experimentally, including its monomeric X-ray structure. Moreover, this radical can be prepared directly from the nitrenium cation by a single electron reduction (E = -0.46 V), and this process is reversible. We envision versatile uses of this radical in synthetic and materials chemistry.