Formation of a Dynamic η2(O,N)-Hydroxylaminato Zirconocene Complex by Nitrosoarene Insertion into a Zr−C σ-Bond

The reaction of dimethylzirconocene with nitrosobenzene gave the hydroxylaminatozirconium complex 6. Its structure in the solid state was characterized as the N-inside isomer [η2(O,N)-ON(CH3)Ph](CH3)ZrCp2 (6a) by X-ray diffraction. Dynamic 1H NMR spectroscopy indicated a rapid enantiomerization process of the chiral system 6a in solution, probably taking place via a rapid equilibration with a reactive η1(O) isomer.