Four – Electron Oxidative Addition of an N=N Double Bond at a Chromium Metallocyclopropene

Abstract

This report describes the synthesis of a pseudo‐tetrahedral chromium alkyne complex supported by a bidentate phosphinimide ligand and its reactivity with azobenzene. Characterization of the former by structural and computational methods reveals an unprecedented extent of alkyne activation by a formal chromium(II) center, suggesting that this complex is best described as a chromium(IV)‐metallocyclopropene. Exposure of this compound to an azobenzene derivative results in the formation of a chromium(VI) diimido complex, which constitutes a rare 4‐electron oxidative addition of an N=N double bond. The isolation of a chromium(IV)‐hydrazido intermediate enabled mechanistic investigations of this challenging bond cleavage process. This work substantiates the notion that terminal phosphinimide ligands can engender first‐row transition metal ions with exceptional reactivity.