DFT calculation as 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.


Table of Contents Page
Table S1.X-ray experimental data and refinement.9  Table S2.Energies of monomeric, dimeric and homoleptic zinc species with Ł ox .
Table S3.Energies of possible equilibrium systems in relation to the most stable zinc dimer: "opened" (Ł ox ZnEt) 2 .Table S4.Energies of monomeric, dimeric and homoleptic zinc species with L ox .
Table S5.Energies of possible equilibrium systems in relation to the most stable zinc dimer: "closed" (L ox ZnEt) 2 .

Figure S17.
Structures of monomeric and dimeric zinc species with Ł T .

Figure S18.
Structures of homoleptic zinc species with Ł T .
Table S6.Energies of monomeric, dimeric and homoleptic zinc species with Ł T .Table S7.Energies of possible equilibrium systems in relation to the most stable zinc monomer: "closed" Ł T ZnEt.Table S8.Energies of monomeric, dimeric and homoleptic zinc species with Ł M .Table S9.Energies of possible equilibrium systems in relation to the most stable zinc monomer: "closed" Ł M ZnEt.Table S10.Energies of ethyl and methoxy zinc species species with Ł T , methanol (MeOH) and ethane (EtH).
Table S11.Energies of possible equilibrium systems in relation to the system: 2 "closed" Ł T ZnEt + 2 MeOH.
Table S12.Energies of ethyl and methoxy zinc species species with Ł T .   . 1 H COSY of (L ox ZnEt) 2 in benzene-d 6 .

Figure S13 .
Figure S13.Structures of monomeric and dimeric zinc species with Ł ox .

Figure S15 .
Figure S15.Structures of monomeric and dimeric zinc species with L ox .

Figure S16 .
Figure S16.Structures of homoleptic zinc species with L ox .

Figure S21 .
Figure S21.Structures of methoxy zinc species with Ł T (schematic on left, DFT optimised on right).

Figure S22 .
Figure S22.Structures of methoxy zinc species with L cy (schematic on left, DFT optimised on right).
Figure S1. 1 H NMR of L ox -H in CDCl 3 .
Figure S9. 1 H NMR of L R L ox Zn 2 Et 2 in benzene-d 6 .

Figure S13 .Figure S14 .
Figure S13.Structures of monomeric and dimeric zinc species with Ł ox (schematic on left, DFT optimised on right).

Figure S15 .Figure S16 .
Figure S15.Structures of monomeric and dimeric zinc species with L ox (schematic on left, DFT optimised on right).

Figure S17 .Figure S18 .
Figure S17.Structures of monomeric and dimeric zinc species with Ł T (schematic on left, DFT optimised on right).

Figure S19 .Figure S20 .
Figure S19.Structures of monomeric and dimeric zinc species with Ł M (schematic on left, DFT optimised on right).

Figure S21 .Figure S22 .
Figure S21.Structures of methoxy zinc species with Ł T (schematic on left, DFT optimised on right).

Table S13 .
Energies of possible equilibrium systems in relation to the system: (L cy ZnEt) 2 + 2 MeOH.

Table S1 .
X-ray experimental data and refinement.

Table S2 .
Energies of monomeric, dimeric and homoleptic zinc species with Ł ox .

Table S3 .
Energies of possible equilibrium systems in relation to the most stable zinc dimer: "opened" (Ł ox ZnEt) 2 .

Table S4 .
Energies of monomeric, dimeric and homoleptic zinc species with L ox .

Table S5 .
Energies of possible equilibrium systems in relation to the most stable zinc dimer: "closed" (L ox ZnEt) 2 .

Table S6 .
Energies of monomeric, dimeric and homoleptic zinc species with Ł T .

Table S7 .
Energies of possible equilibrium systems in relation to the most stable zinc monomer: "closed" Ł T ZnEt.

Table S8 .
Energies of monomeric, dimeric and homoleptic zinc species with Ł M .

Table S9 .
Energies of possible equilibrium systems in relation to the most stable zinc monomer: "closed" Ł M ZnEt.

Table S10 .
Energies of ethyl and methoxy zinc species species with Ł T , methanol (MeOH) and ethane (EtH).