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Updated: Jul 17, 2025

Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides
Published on: May 26, 2019
Four-Electron Oxidative Addition of an N=N Double Bond at a Chromium Metallocyclopropene
Paul Rathke1, Jonathan Rittle1
1College of Chemistry, University of California Berkeley, Berkeley, CA 94720, USA.
Abstract:
This report describes the synthesis of a pseudo-tetrahedral chromium alkyne complex supported by a bidentate phosphinimide ligand and its reactivity with an azobenzene derivative. 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 4,4'-difluoroazobenzene 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.
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