The Triple-Bond Metathesis of Aryldiazonium Salts: A Prospect for Dinitrogen Cleavage.
The {N2 } unit of aryldiazonium salts undergoes unusually facile triple-bond metathesis on treatment with molybdenum or tungsten alkylidyne ate complexes endowed with triphenylsilanolate ligands. The reaction transforms the alkylidyne unit into a nitrile and the aryldiazonium entity into an imido ligand on the metal center, as unambiguously confirmed by X-ray structure analysis of two representative examples. A tungsten nitride ate complex is shown to react analogously. Since the bonding situation of an aryldiazonium salt is similar to that of metal complexes with end-on-bound dinitrogen, in which {N2 }→M σ donation is dominant and electron back donation minimal, the metathesis described herein is thought to be a conceptually novel strategy toward dinitrogen cleavage devoid of any redox steps and, therefore, orthogonal to the established methods.
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr (Germany).
Aaron D
AD
Lackner
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr (Germany). fuerstner@kofo.mpg.de.
Alois
A
Fürstner
alkylidynes; aryldiazonium salts; metathesis; molybdenum; tungsten