Stable Diporphyrinylaminyl Radical and Nitrenium Ion

Abstract

Nitrenium ions, isoelectronic nitrogen counterparts of carbenes, are important intermediates in various biological and chemical processes. Herein we describe the first synthesis and characterization of a stable nitrenium ion without resonance stabilization by adjoining amino groups. Namely, a stable salt of a diporphyrinylnitrenium ion was synthesized by stepwise oxidation of the corresponding diporphyrinylamine through a stable aminyl radical. The nitrenium ion exhibits characteristic features such as a singlet ground state, enhanced double-bond character of the central C-N bonds, no reactivity toward water and methanol, and negative solvatochromic behavior.

Keywords: EPR; aminyl radicals; disproportionation; nitrenium ions; porphyrins.