Ligand coordination controlled by monomer binding: a hint from DFT for stereoselective lactide polymerization

D'Alterio, Massimo Christian; Moccia, Serena; Rusconi, Yolanda; De Rosa, Claudio; Talarico, Giovanni

doi:10.1039/d4cy00937a

Catal. Sci. Technol.

2024

DOI: 10.1039/d4cy00937a

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Ligand coordination controlled by monomer binding: a hint from DFT for stereoselective lactide polymerization

Massimo Christian D'Alterio,

Serena Moccia,

Yolanda Rusconi

et al.

Abstract: Stereoselective ring opening polymerization (ROP) of racemic lactide (rac-LA) is a challenging goal because a rationale connecting catalyst structure and polymer microstructure (as has been established for α-olefin polymerization) is...

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Cited by 2 publications

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Stereoselectivity Control Interplay in Racemic Lactide Polymerization by Achiral Al‐Salen Complexes

Moccia,

D’ Alterio,

Romano

et al. 2024

Macromol. Rapid Commun.

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The origin of stereocontrol in ring opening polymerization (ROP) of racemic lactide (rac‐LA) promoted by achiral aluminium‐based catalysts has been explained through DFT calculations combined with a molecular descriptor (%VBur) and the activation strain model (ASM‐NEDA) analysis. The proposed chain end control (CEC) model suggests that the ligand framework adopts a chiral configuration mimicking the enantiomorphic site control (ESC) while also incorporating control of the last inserted monomer unit. It is found that the ligand wrapping mode around the aluminium centre is dictated by the monomer configuration (R,R‐LA and S,S‐LA). A good correlation with experimental data is achieved only when accounting for the ligand dynamic features and its steric influences, as highlighted by %VBur steric maps and ASM‐NEDA analysis. Understanding the ESC and CEC interplay is an important target for obtaining stereoselective ROP polymerization for the synthesis of biodegradable materials with tailored properties.

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Stereoselectivity Control Interplay in Racemic Lactide Polymerization by Achiral Al‐Salen Complexes

Moccia,

D’ Alterio,

Romano

et al. 2024

Macromol. Rapid Commun.

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Synthesis of Aluminum Complexes Based on 2,6‐Bis(2‐hydroxyphenyl)Pyridines: Efficient Initiators for Ring‐Opening Polymerization of Cyclic Esters

Serova,

Lykov,

Mankaev

et al. 2024

ChemistrySelect

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The search for new initiators based on nontoxic metal complexes, allowing for the controlled production of polycaprolactone (PCL) and polylactide (PLA) is an actual task. In the present work, we report the synthesis of aluminum complexes 6a and 6b based on substituted 2,6‐bis(2‐hydroxyphenyl)pyridine pro‐ligands. The compositions and structures of the novel compounds were established by elemental analysis and 1H, 13C, NMR spectroscopy in the solid state by X‐ray diffraction analysis (6a and 6b). All the synthesized aluminum complexes are monomeric. Complexes 6a and 6b (in presence of benzyl alcohol (BnOH)) turned out to be active in the ring opening polymerization (ROP) of ε‐caprolactone (ε‐CL), L‐, rac‐lactide (L‐, rac‐LA) gave PCL and PLA with high molecular weights. The mechanism of the polymerization reaction for compounds С, 6a, and 6b was also investigated using the density functional theory (DFT) method. The substituent effect analyzed in terms of percent buried volume and non‐covalent interactions. The values of calculated Gibbs free activation energies correspond to the trend found experimentally.

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Ligand coordination controlled by monomer binding: a hint from DFT for stereoselective lactide polymerization

Abstract: Stereoselective ring opening polymerization (ROP) of racemic lactide (rac-LA) is a challenging goal because a rationale connecting catalyst structure and polymer microstructure (as has been established for α-olefin polymerization) is...

Cited by 2 publications

References 46 publications

Stereoselectivity Control Interplay in Racemic Lactide Polymerization by Achiral Al‐Salen Complexes

Stereoselectivity Control Interplay in Racemic Lactide Polymerization by Achiral Al‐Salen Complexes

Synthesis of Aluminum Complexes Based on 2,6‐Bis(2‐hydroxyphenyl)Pyridines: Efficient Initiators for Ring‐Opening Polymerization of Cyclic Esters

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