A Synthetic Cycle for Nitrogen Atom Transfer Featuring a Diruthenium Nitride Intermediate

A new Ru2 azido complex, [Ru2(chp)4N3] (4, chp = 2-chloro-6-hydroxypyridinate), was investigated under photolytic conditions to study the chemical reactivity of the corresponding Ru2 nitride species, [Ru2(chp)4N] (6), towards intermolecular N atom transfer to triphenylphosphane (PPh3). Photolysis of a dichloromethane solution of 4 at λ > 350 nm leads to a characteristic color change from purple to magenta. Upon acidic workup, triphenylphosphanamine chloride ([H2NPPh3]Cl) is produced and [Ru2(chp)4Cl] (5), the precursor to 4, is regenerated. The first stoichiometric cycle for intermolecular N atom transfer from a Ru2 nitride is thus presented.