The synthesis and characterization of LTi(O-i-Pr)(2) (1) and LTiCl(2) (2) complexes containing a new [ONNO]-type tetradentate diamine-diethanolate ligand such as (HOCMe(2)CH(2)NMeCH(2)CH(2)NMeCH(2)CMe(2)OH) (LH(2)) was achieved. Single-crystal X-ray analyses revealed that monomeric complexes 1 and 2 had pseudo-C(2) and pseudo-C(1) symmetric distorted octahedral geometry, respectively. Interestingly, complex 1 has fac-fac geometry for tetradentate L around a Ti centre in both solid and solution, whereas complex 2 has different geometry in solid (mer-fac, C(1)) and solution (fac-fac, C(2)). They are effective catalysts for the controlled ring opening polymerization of L-lactide, as shown by the linearity of the number average of the molecular weight of polylactides versus conversion, as well as narrow PDI values.
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