Functionalization of Alkynes by a (Salen)ruthenium(VI) Nitrido Complex

Exploring new reactivity of metal nitrides is of great interest because it can give insights to N-2 fixation chemistry and provide new methods for nitrogenation of organic substrates. In this work, reaction of a (salen) ruthenium(VI) nitrido complex with various alkynes results in the formation of novel (salen) ruthenium(III) imine complexes. Kinetic and computational studies suggest that the reactions go through an initial ruthenium(IV) aziro intermediate, followed by addition of nucleophiles to give the (salen) ruthenium(III) imine complexes. These unprecedented reactions provide a new pathway for nitrogenation of alkynes based on a metal nitride.