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The role of neutral donor ligands in the isoselective ring-opening polymerization of rac-β-butyrolactone.

ABSTRACT: Isoenriched poly-3-hydroxybutyrate (P3HB) is a biodegradable material with properties similar to isotactic polypropylene, yet efficient routes to this material are lacking after 50+ years of extensive efforts in catalyst design. In this contribution, a novel lanthanum aminobisphenolate catalyst (1-La) can access isoenriched P3HB through the stereospecific ring-opening polymerization (ROP) of rac-β-butyrolactone (rac-BBL). Replacing the tethered donor group of a privileged supporting ligand with a non-coordinating benzyl substituent generates a catalyst whose reactivity and selectivity can be tuned with inexpensive achiral neutral donor ligands (e.g. phosphine oxides, OPR₃). The 1-La/OPR₃ (R = n-octyl, Ph) systems display high activity and are the most isoselective homogeneous catalysts for the ROP of rac-BBL to date (0 °C: P _m = 0.8, TOF ∼190 h^-1). Combined reactivity and spectroscopic studies provide insight into the active catalyst structure and ROP mechanism. Both 1-La(TPPO)2 and a structurally related catalyst with a tethered donor group (2-Y) operate under chain-end stereocontrol; however, 2-RE favors formation of P3HB with opposite tacticity (syndioenriched) and its ROP activity and selectivity are totally unaffected by added neutral donor ligands. Our studies uncover new roles for neutral donor ligands in stereospecific ROP, including suppression of chain-scission events, and point to new opportunities for catalyst design.

SUBMITTER: Dong X

PROVIDER: S-EPMC8163396 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Zinc-Catalyzed Highly Isoselective Ring Opening Polymerization of rac-Lactide.

Project description:A family of chiral zinc amido-oxazolinate complexes are shown to be highly active and isoselective initiators for the ring-opening polymerization (ROP) of rac-lactide, yielding isotactic stereoblock polylactides (PLA) with Pm up to 0.91. This represents the highest isoselectivity observed with zinc-based catalysts for ROP of rac-lactide.

| S-EPMC4105174 | biostudies-literature

Stereoselective Ring-Opening (Co)polymerization of β-Butyrolactone and ε-Decalactone Using an Yttrium Bis(phenolate) Catalytic System.

Project description:An effective route for ring-opening copolymerization of β-butyrolactone (BBL) with ε-decalactone (ε-DL) is reported. Microstructures of the block copolymers characterized by 13C NMR spectroscopy revealed syndiotactic-enriched poly(3-hydroxybutyrate) (PHB) blocks. Several di- and triblock copolymers (PDL-b-PHB and PDL-b-PHB-b-PDL, respectively) were successfully synthesized by sequential addition of the monomers using (salan)Y(III) complexes as catalysts. The results from MALDI-ToF mass spectrometry confirmed the presence of the copolymers. Moreover, thermal properties of the block copolymers were also investigated and showed that the microphase separation of PDL-b-PHB copolymers into PHB- and PDL-rich domains has an impact on the glass transition temperatures of both blocks.

| S-EPMC6541034 | biostudies-literature

Isoselective Lactide Ring Opening Polymerisation using [2]Rotaxane Catalysts.

Project description:Polylactide (PLA) is a fully biodegradable and recyclable plastic, produced from a bio-derived monomer: it is a circular economy plastic. Its properties depend upon its stereochemistry and isotactic PLA shows superior thermal-mechanical performances. Here, a new means to control tacticity by exploiting rotaxane conformational dynamism is described. Dynamic achiral [2]rotaxanes can show high isoselectivity (Pi =0.8, 298 K) without requiring any chiral additives and enchain by a chain end control mechanism. The organocatalytic dynamic stereoselectivity is likely applicable to other small-molecule and polymerization catalyses.

| S-EPMC6519244 | biostudies-literature

Ring-Opening Polymerization of rac-Lactide with Aluminum Chiral Anilido-Oxazolinate Complexes.

Project description:A series of dimethylaluminum complexes (L1a-i )AlMe2 (2a-i, where HL1a-i = 2-(2'-ArNH)phenyl-4-R1-oxazoline) bearing chiral, bidentate anilido-oxazolinate ligands have been prepared and characterized. Six of the complexes, in the presence of an alcohol cocatalyst, are shown to be active initiators for the stereoselective ring-opening polymerization of rac-lactide in toluene solution and under bulk conditions, yielding polylactides with a range of tacticity from slightly isotactic to moderately heterotactic. The reactivity and selectivity of these catalysts are discussed on the basis of the effect of their substituents.

| S-EPMC4036730 | biostudies-literature

It is Better with Salt: Aqueous Ring-Opening Metathesis Polymerization at Neutral pH.

Project description:Aqueous ring-opening metathesis polymerization (ROMP) is a powerful tool for polymer synthesis under environmentally friendly conditions, functionalization of biomacromolecules, and preparation of polymeric nanoparticles via ROMP-induced self-assembly (ROMPISA). Although new water-soluble Ru-based metathesis catalysts have been developed and evaluated for their efficiency in mediating cross metathesis (CM) and ring-closing metathesis (RCM) reactions, little is known with regards to their catalytic activity and stability during aqueous ROMP. Here, we investigate the influence of solution pH, the presence of salt additives, and catalyst loading on ROMP monomer conversion and catalyst lifetime. We find that ROMP in aqueous media is particularly sensitive to chloride ion concentration and propose that this sensitivity originates from chloride ligand displacement by hydroxide or H2O at the Ru center, which reversibly generates an unstable and metathesis inactive complex. The formation of this Ru-(OH)n complex not only reduces monomer conversion and catalyst lifetime but also influences polymer microstructure. However, we find that the addition of chloride salts dramatically improves ROMP conversion and control. By carrying out aqueous ROMP in the presence of various chloride sources such as NaCl, KCl, or tetrabutylammonium chloride, we show that diblock copolymers can be readily synthesized via ROMPISA in solutions with high concentrations of neutral H2O (i.e., 90 v/v%) and relatively low concentrations of catalyst (i.e., 1 mol %). The capability to conduct aqueous ROMP at neutral pH is anticipated to enable new research avenues, particularly for applications in biological media, where the unique characteristics of ROMP provide distinct advantages over other polymerization strategies.

| S-EPMC7426906 | biostudies-literature

Cationic indium catalysts for ring opening polymerization: tuning reactivity with hemilabile ligands.

Project description:This is a comprehensive study of the effects of rationally designed hemilabile ligands on the stability, reactivity, and change in catalytic behavior of indium complexes. We report cationic alkyl indium complexes supported by a family of hemi-salen type ligands bearing hemilabile thiophenyl (2a), furfuryl (2b) and pyridyl (2c) pendant donor arms. Shelf-life and stability of these complexes followed the trend 2a < 2b < 2c, showing direct correlation to the affinity of the pendant donor group to the indium center. Reactivity towards polymerization of epichlorohydrin and cyclohexene oxide followed the trend 2a > 2b > 2c with control of polymerization following an inverse relationship to reactivity. Surprisingly, 2c polymerized racemic lactide without an external initiator, likely through an alkyl-initiated coordination-insertion mechanism.

| S-EPMC8159295 | biostudies-literature

Palladium complexes containing imino phenoxide ligands: synthesis, luminescence, and their use as catalysts for the ring-opening polymerization of rac-lactide.

Project description:AbstractThe preparation, structural characterization, luminescence, and catalytic activity of three palladium(II) complexes bearing imino phenoxide ligands are reported. The X-ray studies revealed that the complexes are mononuclear with palladium centres coordinated in a square-planar coordination environment. Two of the complexes are emissive in solution at room temperature. The catalytic activities towards the ring-opening polymerization of rac-lactide (rac-LA) were tested. Polymers with moderate molecular weights and relatively broad dispersity (Ð) were obtained. Kinetic studies revealed that the polymerization followed first-order kinetics.Graphical abstract

| S-EPMC5906497 | biostudies-literature

Isoselective Polymerization of rac-Lactide by Aluminum Complexes of N-Heterocyclic Carbene-Phosphinidene Adducts.

Project description:The N-heterocyclic carbene-phosphinidene adducts (NHC)PH were reacted with AlMe3 in toluene to afford the monoaluminum complexes [{(IDipp)PH}AlMe3 ] and [{(IMes)PH}AlMe3 ] (IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene, IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene). In contrast, the dialuminum complex [{(Me IMes)PH}(AlMe3 )2 ] was obtained for Me IMes=1,3-bis(2,4,6-trimethylphenyl)-4,5-dimethylimidazolin-2-ylidene. These complexes served as initiators for the efficient ring-opening polymerization of rac-lactide in toluene at 60 °C. High degrees of isoselectivity were found for the poly(rac-lactide) obtained in the presence of the monoaluminum complexes (Pm up to 0.92, Tm up to 191 °C), whereas almost atactic polymers were produced by the dialuminum complex. Detailed mechanistic studies reveal that the polymerization proceeds via a coordination-insertion mechanism with the carbene-phosphinidene ligands acting as stereodirecting groups.

| S-EPMC8048956 | biostudies-literature

Living ring-opening polymerization of β-butyrolactone initiated by mononuclear zirconium compounds containing sterically hindered N,O-chelate and anionic dimethylamide ligands† † Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d3ra00338h

Project description:The ring-opening polymerization of β-lactones into polyhydroxyalkanoates (PHA), biodegradable polymers with high molecular weight and narrow polydispersity, is of significant interest. The mononuclear zirconium compound containing sterically hindered N,O-chelate and anionic dimethylamide ligands was used as an initiator for the polymerization of β-butyrolactone (BBL), resulting in polyhydroxylbutyrate (PHB) with a number-average molecular weight of 12 000 g mol−1. Kinetic studies demonstrate a first-order dependence on β-butyrolactone (BBL) concentration at room temperature, accompanied by narrow molecular weight distributions (ca. 1.03–1.07), indicating a well-controlled living polymerization. The ring-opening polymerization of β-lactones into polyhydroxyalkanoates (PHA), biodegradable polymers with high molecular weight and narrow polydispersity, is of significant interest.

| S-EPMC10068430 | biostudies-literature

Copper(II) complexes with imino phenoxide ligands: synthesis, characterization, and their application as catalysts for the ring-opening polymerization of rac-lactide.

Project description:Four new copper complexes based on bidentate imino phenoxide ligands were synthesized and characterized by IR, UV-Vis spectroscopy, ESI mass spectrometry, single crystal X-ray diffraction, and electrochemistry. The crystal structures revealed that the copper(II) atoms are surrounded by phenolate oxygen and imine nitrogen atoms of two ligands in a distorted square-planar geometry. The existence of ligand-centered, as well as Cu(II)-centered quasi-reversible and reversible redox reactions are observed in the cyclic voltammetry experiments of all the complexes. All complexes are able to catalyze the ring-opening polymerization of rac-lactide yielding polymers with moderate molecular weights and moderately broad molecular weight distributions.

| S-EPMC5063905 | biostudies-other

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