Titanium(IV) derivatives of the chelating monoanionic aryldiamine ligand [C 6 H 3 (CH 2 -NMe 2 ) 2 -2,6] -(abbreviated as NCN) are prepared by treating [TiCl 3 (OR)] (R ) i-Pr, C 6 H 4 -OMe-4) with [Li(NCN)] 2 . [TiCl 2 (NCN)(O-i-Pr)] is smoothly methylated by methyllithium in toluene to give [TiClMe(NCN)(O-i-Pr)] and [TiMe 2 (NCN)(O-i-Pr)]. Enhancement of the Lewis acidity of the titanium center has been studied by substituting chloro ligands for triflato ligands to give [TiCl(NCN)(O-i-Pr)(OTf)] and [Ti(NCN)(O-i-Pr)(OTf) 2 ]. X-ray studies of the dichloride and triflate complexes feature η 3 -pseudofacial and η 3 -meridional bonding modes for the NCN ligand, respectively. These different NCN bonding modes are explained in terms of the trans influence of the alkoxy and triflato ligands. A rare example of an organo titanium(IV) complex with a seven-coordinate titanium center is observed in the bis(triflate) complex as a result of bidentate O,O′-bonding mode of the triflato anion to one titanium center that is unprecedented in early transition metal chemistry. The triflato ligands exhibit a strong covalent bonding to titanium both in the solid state and in solution; the latter is demonstrated by the observation that cationic species are not formed upon addition of Lewis bases like THF, acetonitrile, and 1,2-bis(dimethylamino)ethane.