The reaction of Ti(O i Pr) 4, diisopropyl ( R, R)-tartrate and N, N′-di(trifluoromethylsulfonyl)ethane-1,2-diamine in 1:2:1 ratio provided a symmetric, dinuclear complex of formula [Ti(η 2- dipt)(η 2-H dipt)(O i Pr)] 2 (where H 2 dipt is diisopropyl tartrate), in which each metal bears one O i Pr ligand, a chelating tartrate diolate bridging the two metals, and a second, univalent tartrate unit in a novel binding mode, attached through alkoxy and ester carbonyl oxygens. This species appears to be stabilized through hydrogen bonding with the disulfonamide. The configuration at Ti deduced by NMR spectral information coincides with that calculated to be the most stable. In the absence of the disulfonamide, the data are consistent with an equilibrium between this complex, free tartrate and a condensation product of formula Ti 4( dipt) 5(H dipt) 2(O i Pr) 4 which features an η 2,η 2-tartrate linking two Ti 2(η 2- dipt) 2(η 2-H dipt)(O i Pr) 2 units. The relationship between these species and the Kagan and Modena catalysts for the asymmetric oxidation of sulfides is discussed.