Investigating the Ring-Opening Polymerization Activity of Niobium and Tantalum Ethoxides Supported by Phenoxyimine Ligands
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ABSTRACT:
SUBMITTER: Plaman A
PROVIDER: S-EPMC9281319 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Aluminum complexes containing [RP(O)(2-O-3,5-tBu2C6H2)2]2- [R = tBu (3a), Ph (3b)] have been synthesized, structurally characterized, and their reactivity studied in comparison with those of their [RP(2-O-3,5-tBu2C6H2)2]2- [R = tBu (2a), Ph (2b)] analogs. Treating AlMe3 with one equiv of H2[3a-b] in THF at 0°C affords quantitatively [3a-b]AlMe, subsequent reactions of which with benzyl alcohol in THF at 25°C generate {[3a-b]Al(?2-OCH2Ph)}2. The methyl [3a-b]AlMe and the benzyloxide {[3a-b]Al(?2-OCH2Ph)}2 are all active for catalytic ring-opening polymerization (ROP) of ?-caprolactone and rac-lactide (rac-LA). Controlled experiments reveal that {[3a]Al(?2-OCH2Ph)}2 is competent in living polymerization. Kinetic studies indicate that [3a]AlMe, in the presence of benzyl alcohol, catalyzes ROP of rac-LA at a rate faster than [3b]AlMe and [2a]AlMe(THF) by a factor of 1.8 and 23.6, respectively, highlighting the profound reactivity enhancement in ROP catalysis by varying the P-substituents of these biphenolate complexes of aluminum.
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Project description:Well-defined molecular brushes bearing polypeptides as side chains were prepared by a "grafting through" synthetic strategy with two-dimensional control over the brush molecular architectures. By integrating N-carboxyanhydride ring-opening polymerizations (NCA ROPs) and ring-opening metathesis polymerizations (ROMPs), desirable segment lengths of polypeptide side chains and polynorbornene brush backbones were independently constructed in controlled manners. The N2 flow accelerated NCA ROP was utilized to prepare polypeptide macromonomers with different lengths initiated from a norbornene-based primary amine, and those macromonomers were then polymerized via ROMP. It was found that a mixture of dichloromethane and an ionic liquid were required as the solvent system to allow for construction of molecular brush polymers having densely-grafted peptide chains emanating from a polynorbornene backbone, poly(norbornene-graft-poly(?-benzyl-l-aspartate)) (P(NB-g-PBLA)). Highly efficient postpolymerization modification was achieved by aminolysis of PBLA side chains for facile installment of functional moieties onto the molecular brushes.
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Project description:For the first time, the controlled ring-opening polymerization (ROP) of ?-thionocaprolactone (tnCL) is conducted. The organocatalytic ROP of tnCL occurs without carbonyl scrambling, leading to homopoly(?-thionocaprolactone) (PtnCL). The ROP by base catalysts alone is proposed to proceed via a nucleophilic mechanism, while the addition of an H-bond donating thiourea (TU) is shown to provide excellent reaction control. The increased reaction control provided by the TU occurs in the virtual absence of binding between tnCL and TU, and a mechanistic account for this observation is discussed. The monomer ring strain is measured and found to be similar to ?-valerolactone (VL). Copolymers with VL are synthesized, and the resulting analysis of the copolymer materials properties provides the only known physical characterizations of poly(thio(no)ester-co-ester)s.
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Project description:The need for polymers for high-end applications, coupled with the desire to mimic nature's macromolecular machinery fuels the development of innovative synthetic strategies every year. The recently acquired macromolecular-synthetic tools increase the precision and enable the synthesis of polymers with high control and low dispersity. However, regardless of the specificity, the polymerization behavior is highly dependent on the monomeric structure. This is particularly true for the ring-opening polymerization of lactones, in which the ring size and degree of substitution highly influence the polymer formation properties. In other words, there are two important factors to contemplate when considering the particular polymerization behavior of a specific monomer: catalytic specificity and thermodynamic equilibrium behavior. This perspective focuses on the latter and undertakes a holistic approach among the different lactones with regard to the equilibrium thermodynamic polymerization behavior and its relation to polymer synthesis. This is summarized in a monomeric overview diagram that acts as a presynthetic directional cursor for synthesizing highly specific macromolecules; the means by which monomer equilibrium conversion relates to starting temperature, concentration, ring size, degree of substitution, and its implications for polymerization behavior are discussed. These discussions emphasize the importance of considering not only the catalytic system but also the monomer size and structure relations to thermodynamic equilibrium behavior. The thermodynamic equilibrium behavior relation with a monomer structure offers an additional layer of complexity to our molecular toolbox and, if it is harnessed accordingly, enables a powerful route to both monomer formation and intentional macromolecular design.
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Project description:Organocatalysts typically used for the ring-opening polymerization (ROP) of cyclic ester monomers are applied to a thiolactone, ?-thiocaprolactone (tCL). In the absence of an H-bond donor, a nucleophilic polymerization mechanism is proposed. Despite the decreased ability of thioesters and thiols (versus esters and alcohols) to H-bond, H-bonding organocatalysts-a thiourea in combination with an H-bond accepting base-are also effective for the ROP of tCL. The increased nucleophilicity of thiols (versus alcohols) is implicated in the increased Mw/Mn of the poly(thiocaprolactone) versus poly(caprolactone), but deleterious transesterification is suppressed in the presence of a thiourea. The thioester monomer, tCL, is shown to be thermodynamically similar to ?-caprolactam but kinetically similar to ?-caprolactone.
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Project description:Biodegradable polyesters with various tacticities have been synthesized by means of stereoselective ring-opening polymerization of racemic lactide and ?-lactones but with limited side-chain groups. However, stereoselective synthesis of functional polyesters remains challenging from O-carboxyanhydrides that have abundant pendant side-chain functional groups. Herein we report a powerful strategy to synthesize stereoblock polyesters by stereoselective ring-opening polymerization of racemic O-carboxyanhydrides with the use of photoredox Ni/Ir catalysts and a selected Zn complex with an achiral ligand. The obtained stereoblock copolymers are highly isotactic with high molecular weights (?>?70?kDa) and narrow molecular weight distributions (Mw/Mn?<?1.1), and they display distinct melting temperatures that are similar to their stereocomplex counterparts. Furthermore, in one-pot photoredox copolymerization of two different O-carboxyanhydrides, the use of such Zn complex mediates kinetic resolution of the comonomers during enchainment and shows a chirality preference that allows for the synthesis of gradient copolymers.
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Project description:A family of different substituents aza(oxazoline) ligand-based zinc and magnesium complexes were synthesized. These complexes can catalyze ring opening polymerization of ?-caprolactone (?-CL) and lactide (LA) to produce poly-?-caprolactone and polylactide with good conversions. Polymerization studies showed that the zinc complexes 1a-4a had moderate activity toward LA and ?-CL polymerization. In situ IR spectroscopy research of zinc complexes showed that the N-donor group-substituted complexes had higher activity than that of the O-ether donor group. The substituted analogies and the flexibility of the amino backbone had a distinct influence on the activity of LA and ?-CL polymerization. The alternates of zinc with magnesium produced complexes 5a-8a, which achieved an obviously increased polymerization activity. Among these magnesium complexes, 7a showed the highest activity in the polymerization of LA. At [M]/[cat] = 1000, the reaction progress was stabilized in 5 min with up to 97% conversion of a monomer at ambient temperature.
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Project description: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.
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Project description:The living ring-opening metathesis polymerization (ROMP) of an unsaturated twisted amide using the third-generation Grubbs initiator is described. Unlike prior examples of ROMP monomers that rely on angular or steric strain for propagation, this system is driven by resonance destabilization of the amide that arises from geometric constraints of the bicyclic framework. Upon ring-opening, the amide can rotate and rehybridize to give a stabilized and planar conjugated system that promotes living propagation. The absence of other strain elements in the twisted amide is supported by the inability of a carbon analogue of the monomer to polymerize and computational studies that find resonance destabilization accounts for 11.3 kcal mol-1 of the overall 12.0 kcal mol-1 ring strain. The twisted amide polymerization is capable of preparing high molecular weight polymers rapidly at room temperature, and post-polymerization modification combined with 2D NMR spectroscopy confirms a regioirregular polymer microstructure.
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