Abstract
Di-µ-chloro-dichlorotetrakis[phenyl(2-pyridyl)amido]dizirconium(IV), trichlorobis[phenyl(2-pyridyl)amido]niobium(V) and trichlorobis[phenyl(2-pyridyl)amido]tantalum(V) have been synthesized in a direct reaction between 2-(phenylamino)pyridine and the appropriate metal halide under reflux in toluene. The use of butyllithium was rejected because of the formation of the unreactive ligand adduct bis[2-(phenylamino)pyridine]bis[phenyl(2-pyridyl)amido]dilithium. Single-crystal structures were determined for all four compounds. The niobium and tantalum complexes are monomeric in the solid state, whereas the zirconium complex is a dimer with two bridging chloride ligands. The amide is didentate with one σ- and one π-donor bond. The chelate rings formed have narrow N–M–N angles, around 60°. The co-ordination spheres around the transition metals are pseudo-pentagonal bipyramids.

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