Exploring enantiopure zinc-scorpionates as catalysts for the preparation of polylactides, cyclic carbonates, and polycarbonates.

New and simple ligand design strategies for the preparation of versatile metal-based catalysts capable of operating under greener and eco-friendly conditions in several industrially attractive processes are in high demand for society development. We present the first nucleophilic addition of an organolithium to ketenimines which incorporates a stereogenic centre in an N-donor atom to prepare new enantiopure NNN-donor scorpionates. We have also verified its potential utility as a valuable scaffold for chirality induction through the preparation of inexpensive, non-toxic and asymmetric zinc complexes. The pro-ligands and the corresponding zinc-based complexes have been characterized by X-ray diffraction studies. DFT studies were carried out to rationalize the different complexation abilities of these pro-ligands. These complexes have proved to act as highly efficient catalysts for a variety of sustainable bioresourced processes that are industrially attractive, with a wide substrate scope. Thus, complex 7 behaves as a highly efficient initiator for the well-behaved living ring-opening polymerization (ROP) of rac -lactide under very mild conditions. The PLA materials produced exhibited enhanced levels of isoselectivity, comparable to the highest value reported so far for zinc-based catalysts ( P i = 0.88). In addition, the combination of 7 with onium halide salts functioned as a very active and selective catalyst for CO 2 fixation into five-membered cyclic carbonates through the cycloaddition of CO 2 into epoxides under very mild and solvent-free conditions, reaching very good to excellent conversions (TOF = 227 h -1 ). Furthermore, this bicomponent system exhibits a broad substrate scope and functional group tolerance, including mono- and di-substituted epoxides, as well as the very challenging bio-renewable tri-substituted terpene-derived cis / trans -limonene oxide, whose reaction proceeds with high stereoselectivity. Finally, complex 7 also achieved high activity and selectivity as a one-component initiator for the synthesis of poly(cyclohexene carbonate)s via ring-opening copolymerization (ROCOP) of cyclohexene oxide and CO 2 under very soft conditions, affording materials with narrow dispersity values.