DFT calculations as a ligand toolbox for the synthesis of active initiators for ROP of cyclic esters.

New heteroleptic zinc dimeric complexes bearing an aminophenolate ligand of a single-site initiator framework were synthesized and characterized by spectroscopic methods, X-ray analysis, and DFT calculations. The theoretical study, verified by the experimental data, explains the catalytic behaviour in the ROP of lactide in the examined zinc complexes. The presented simple DFT protocol constitutes a valuable method for the qualification of the ancillary ligand to rationally design new complexes to improve their catalytic activity.

Zebra reaction or the recipe for the synthesis of heterodimeric zinc complexes.

A series of asymmetric heterodimeric zinc complexes have been synthesized in a direct reaction between conformationally flexible chiral/achiral homodimers. The cooperative activity of steric factors and coordination codes resulted in an intriguing chiral self-sorting process. Herein, we are reporting our recent exploration of the first example of such a type of reaction.

Designing ancillary ligands for heteroleptic/homoleptic zinc complex formation: synthesis, structures and application in ROP of lactides.

Synthesis and characterization of a series of new amino-phenol/naphthol ligands (L(1,2)-H) have been developed and their respective zinc complexes ( 1 and 2-Zn ) have been synthesized. The molecular structures of L(1)-H and 1, 2-Zn were explored in detail by NMR, single-crystal X-ray studies and DFT calculations, which confirmed the existence of complexes as stabile dimers both in a solution and in the solid state. All complexes mediate the ring-opening polymerization (ROP) of lactide highly efficiently, at room temperature, in a controlled fashion. The influence of the architecture of the ligand on the desired homo/heteroleptic complex formation, as well as the relationship between the initiator design and the catalytic activity have been investigated.