Reactions of ligating dinitrogen to form carbon–nitrogen bonds

Abstract

The reactions of [M(N₂)₂(dppe)₂][M = MO or W; dppe = 1,2-bis(diphenylphosphino)ethane] with alkyl bromides, acyl chlorides, or aroyl chlorides, under irradiation, lead to organohydrazido(2–)- and organodiazenido-complexes. Complexes [ReCl(N₂)(PMe₂Ph)₄] and [ReCl(N₂)(py)(PMe₂Ph)₃](py = pyridine) can be acylated but not alkylated at the dinitrogen, but in [OsCl₂(N₂)(PMe₂Ph)₄] dinitrogen is inactive even to acid chlorides. The reactivity of dinitrogen in its complexes decreases along the third Transition Series in the order W > Re > Os.