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N-Arylamido complexes of zirconium in which the amido functional group is attached to an o-(alkyliminoethyl) substituted aromatic ring, have been synthesised by salt elimination reactions and characterised by spectroscopic and diffraction methods; they are analogous to the N-silylamido species recently reported (Dalton Trans., 2002, 3290–3299). The ligands 2-[CyNC(CH3)]C6H4N(H)(xyl), LxylH, and 2-[CyNC(CH3)]C6H4N(H)(mes) LmesH, Cy = C6H11, xyl = 3,5-Me2C6H3 mes = 2,4,6-Me3C6H2, were prepared in good yields by Buchwald–Hartwig amination of the arylbromides with 2-[CyNC(CH3)]C6H4NH2. Reaction of LmesLi with Zr(NEt2)2Cl2(thf)2 gave after chloride substitution the arylamido ketimino complex LmesZr(NEt2)2Cl 1; variable amounts of the arylamido vinylamido complex 2 were also obtained. Interaction of LmesLi or LxylLi with Ti(NMe2)2Cl2 gave rise to the tripodal bis-amido amino complexes 5 and 6 possibly formed by ligand rearrangement involving migration of the dimethylamido group to the ketimino carbon.
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