Add time:08/11/2019         Source:sciencedirect.com

The reactivity pattern of the 16-electron species [M(Cp)2Cl2] (M = Zr, Hf; Cp− = η5-C5H5−) and [Ti(MeCp)2Cl2] (MeCp− = η5-C5H4CH3−) towards the dipicolinate(−2) (dipic2−) ligand under mild (ambient temperature) and convenient (aerobic reactions, aqueous media) conditions have been investigated. The syntheses, molecular structures and spectroscopic (IR, 1H NMR) characterization are reported for the 18-electron products [Zr(Cp)2(dipic)] (1), [Hf(Cp)2(dipic)] (2) and [Ti(MeCp)2(dipic)] (3). The dipic2− ion behaves as N,O,O′-chelating ligand in the three complexes, while the centroids of the Cp− (1, 2) and MeCp− (3) rings formally occupy the fourth and fifth coordination sites about the central metal. The two identical/very similar bite angles of only ∼70° make the dipic2− ligand particularly suited to form stable metallocene derivatives with 5-coordinate geometry. IR and 1H NMR data are discussed in terms of the known structures and the tridentate chelating mode of the dipic2− ligand.

► Bis(η5-cyclopentadienyl)(dipicolinato)zirconium(IV). ► Bis(η5-cyclopentadienyl)(dipicolinato)hafnium(IV). ► Bis(η5-methylcyclopentadienyl)(dipicolinato)titanium(IV). ► Reactivity of Group 4 metallocene dichlorides.

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