Factors affecting the dimerization of persistent nitrogen‐centered 1‐phenyl urazole radicals to tetrazanes

1‐Phenyl urazole radicals are persistent air‐stable nitrogen‐centered radicals that engage in an equilibrium with the corresponding N―N tetrazane dimers in solution. While the equilibrium typically weakly favors the dimer form, for some 1‐phenyl urazole radicals bearing substituents at the ortho position of the benzene ring, the equilibrium instead strongly favors the dimer form. With the recent surge of interest in the properties and potential applications of heterocyclic radicals, the factors that affect this equilibrium are important to determine. We examined the effect of the extent of ortho substitution (none, 1, or 2 substituents) on the equilibrium by experimentally using variable temperature 1 H nuclear magnetic resonance and UV‐visible spectroscopy in addition to supporting computational investigations at the (U)B3LYP/6‐311G(d,p) level of theory. We confirmed that the equilibrium generally favored the dimer in all cases. However, the equilibrium was more favorable towards dimer formation for urazole radicals substituted with 1 and 2 ortho substituents on the aromatic ring. The activation enthalpies for dissociation of singly substituted dimers were greater than that for dimers without ortho substituents, but lower than that for doubly substituted dimers. The greater preference for dimer formation for the ortho ‐substituted urazole radicals is attributed to a greater enthalpic advantage for N―N bond formation. This advantage may be traced to a higher concentration of spin density on the urazole unit of the radicals and a lesser deformation energy required for N―N bond formation.