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

Abstract

Abstract A new Ru 2 azido complex, [Ru 2 (chp) 4 N 3 ] ( 4 , chp = 2‐chloro‐6‐hydroxypyridinate), was investigated under photolytic conditions to study the chemical reactivity of the corresponding Ru 2 nitride species, [Ru 2 (chp) 4 N] ( 6 ), towards intermolecular N atom transfer to triphenylphosphane (PPh 3 ). 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 ([H 2 NPPh 3 ]Cl) is produced and [Ru 2 (chp) 4 Cl] ( 5 ), the precursor to 4 , is regenerated. The first stoichiometric cycle for intermolecular N atom transfer from a Ru 2 nitride is thus presented.