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The synthesis and characterization of triazenido complexes of the group IV metals zirconium and hafnium is reported. The reaction of the group IV pentafulvene complexes Cp*(π-η5:σ-η1-pentafulvene)-zirconium(IV) and -hafnium(IV)chlorides with the sterically demanding 2,6-dimesitylphenyl azide results in the insertion of the γ-nitrogen atom of the ligand precursor into the polarized M-Cexo (Cexo: exocyclic carbon atom) bond of the pentafulvene ligand, forming a formal Cp,N,N tridentate ligand system. The molecular structures of the furnished complexes reveal the rare κ1N coordination of the γ-nitrogen atom to the zirconium or hafnium center along with a localized Nα-Nβ double bond. Unusually, in one case, the ligand system shows additional coordination of the α-nitrogen atom to the central metal atom and well-balanced N-N distances, thus, forming the chelating κ2N,N coordination mode of the triazenido ligand. The potential use of the formed complexes as precursors for cationic group IV cationic complexes was investigated by reaction with methyl lithium.

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