Zuschrift
The Triple-Bond Metathesis of Aryldiazonium Salts: A Prospect for Dinitrogen Cleavage
Dr. Aaron D. Lackner,
Prof. Alois Fürstner,
Dr. Aaron D. Lackner
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr (Germany)
Search for more papers by this authorCorresponding Author
Prof. Alois Fürstner
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr (Germany)
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr (Germany)Search for more papers by this authorDr. Aaron D. Lackner,
Prof. Alois Fürstner,
Dr. Aaron D. Lackner
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr (Germany)
Search for more papers by this authorCorresponding Author
Prof. Alois Fürstner
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr (Germany)
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr (Germany)Search for more papers by this authorAbstract
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.
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