Synthesis and Reactivity of an Anionic Diazoolefin

Bent (hetero)allenes such as carbodicarbenes and carbodiphosphoranes can act as neutral C-donor ligands, and diverse applications in coordination chemistry have been reported. N-Heterocyclic diazoolefins are heterocumulenes, which can function in a similar fashion as L-type ligands. Herein, we describe the synthesis and the reactivity of an anionic diazoolefin. This compound displays distinct reactivity compared to neutral diazoolefins, as evidenced by the preparation of diazo compounds via protonation, alkylation, or silylation. The anionic diazoolefin can be employed as an ambidentate, X-type ligand in salt metathesis reactions with metal halide complexes. Extrusion of dinitrogen was observed in a reaction with PCl(NiPr2)(2), resulting in a stable phosphinocarbene.

Automated summary

Bent (hetero)allenes, such as carbodicarbenes and carbodiphosphoranes, have diverse applications in coordination chemistry as neutral C-donor ligands. N-Heterocyclic diazoolefins function similarly to L-type ligands, and in this study, the synthesis and reactivity of anionic diazoolefin are described. The anionic diazoolefin displays distinct reactivity, allowing for the preparation of diazo compounds via protonation, alkylation, or silylation. It can also be employed as an ambidentate, X-type ligand in salt metathesis reactions with metal halide complexes, resulting in the formation of a stable phosphinocarbene through the extrusion of dinitrogen.