Ti and Zr complexes bearing guanidine-phenolate ligands: coordination chemistry and polymerization studies

A series of group 4 bis(isopropoxide) complexes M[N^O] 2 (O i Pr) 2 , stabilized by guanidine-phenolate N^O ligands, have been prepared and used as catalysts for the polymerization of unpurified rac -lactide under solvent-free conditions at 130 °C. The resulting polylactic acid (PLA) presented heterotactic bias ( P r = 0.56-0.62) with molecular weights similar to those obtained in control experiments with Zr(O i Pr) 4 · i PrOH, Ti(O i Pr) 4 , and Sn(Oct) 2 . The molecular weights were lower than expected for living polymerization due to chain transfer and/or transesterification. Zr complexes were more active than the Ti homologues, with rate constants ranging from 1.17-3.21 × 10 −4 s −1 , comparable to that observed with the free guanidine-phenol ligands. The corresponding bis(guanidine-phenolate) titanium dichloride complexes Ti[N^O] 2 Cl 2 were also prepared and tested in ethylene polymerization. The low activity (up to 1.1 kg PE mol −1 h −1 ) was associated to the strong electron-donating ability of the guanidine moiety and to the trans-N , N-cis-O , O-cis-Cl , Cl coordination mode of the guanidine-phenolate ligand. Ti and Zr complexes of guanidine-phenolate ligands were evaluated in the polymerization of rac -lactide and ethylene.