o-(Cyclohexyliminoethyl)(arylamido)benzene and related complexes of zirconium and titanium. The non-innocence of the ketimino functionality.

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-[CyN=C(CH(3))]C(6)H(4)N(H)(xyl), L(xyl)H, and 2-[CyN=C(CH(3))]C(6)H(4)N(H)(mes) L(mes)H, Cy = C(6)H(11), xyl = 3,5-Me(2)C(6)H(3) mes = 2,4,6-Me(3)C(6)H(2), were prepared in good yields by Buchwald-Hartwig amination of the arylbromides with 2-[CyN=C(CH(3))]C(6)H(4)NH(2). Reaction of L(mes)Li with Zr(NEt(2))(2)Cl(2)(thf)(2) gave after chloride substitution the arylamido ketimino complex L(mes)Zr(NEt(2))(2)Cl 1; variable amounts of the arylamido vinylamido complex 2 were also obtained. Interaction of L(mes)Li or L(xyl)Li with Ti(NMe(2))(2)Cl(2) 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.