Titanium and Vanadium Complexes of Tridentate Phenoxy-Imine and Phenoxy-Amine Ligands and Their Application in the Ring-Opening Polymerization of Cyclic Esters.

Phenoxy-imine and phenoxy-amine proligands, with the additional OH donor groups 2,4-(t)Bu(2)-6-(2-CH(2)(OH)-C(6)H(4)N=CH)C(6)H(3)OH (L(1)H(2)), 6-(2-CH(2)(OH)-C(6)H(4)N=CH)C(6)H(3)OH (L(2)H(2)), and 2,4-(t)Bu(2)-6-(2-CH(2)(OH)-C(6)H(4)NH-CH)C(6)H(3)OH (L(3)H(2)), were synthesized and their titanium (Ti-L(1)-Ti-L(3)) and vanadium (V-L(1)-V-L(2)) complexes were prepared in reactions with Ti(O(i)Pr)(4) and VO(O(i)Pr)(3), respectively. All new compounds were characterized with the use of FTIR, (1)H, and (13)C NMR spectroscopy; X-ray crystallography was also used to study proligands. All the complexes proved to be active catalysts in the ring-opening polymerization (ROP) of ε-caprolactone, rac-lactide, and L-lactide in the melt. The effects of the complex structure (transition metal type, presence of tBu substituents, and type of nitrogen donor group), as well as the polymerization time and temperature, on the monomer conversion and polymer properties were investigated in detail.