Ring opening polymerization of <scp>d</scp>,<scp>l</scp>-lactide and ε-caprolactone catalysed by (pyrazol-1-yl)copper(<scp>ii</scp>) carboxylate complexes

Appavoo, Divambal; Spencer, Lara C.; Guzei, Ilia A.; Gómez‐García, Carlos J.; Wyk, Juanita L. van; Darkwa, James

doi:10.1039/d1ra00339a

Cited by 6 publications

(3 citation statements)

References 70 publications

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“…The Cu1•••Cu1' distance in the paddle-wheel geometry is 2.621(1) Å, corresponding to a weak cuprophilic interaction. This distance falls within the range observed for other similar species [35]. Consequently, the geometry of the paddle-wheel Cu2 unit can be described as a pseudooctahedral species.…”

Section: Description Of the Crystal Structuressupporting

confidence: 83%

Anion-Dependent Cu(II) Coordination Polymers: Geometric, Magnetic and Luminescent Properties

et al. 2022

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A one-dimensional (1D) coordination polymer [Cu2(bpba)(CH3COO)4] (1) and a two-dimensional (2D) coordination polymer [Cu(bpba)2(H2O)(NO3)](NO3)∙2H2O∙MeOH (2) were synthesized by the reaction between Cu(CH3COO)2∙H2O/Cu(NO3)2∙3H2O and bis(4-pyridyl)benzylamine (bpba). The Cu(II) ions of 1 and 2 have distorted-square pyramidal coordination with a paddle-wheel structure and an octahedral geometry, respectively. By coordinating the Cu(II) ions and bpba ligands, 1 and 2 formed zigzag 1D and puckered 2D coordination polymers, respectively. Polymer 1 exhibits strong emissions at 355 and 466 nm, whereas polymer 2 exhibits strong emissions only at 464 nm. The emissions are strongly dependent on the geometry of the Cu(II) ions linked by the bpba and anionic ligands. Polymer 1 exhibits a very strong antiferromagnetic interaction within the paddle-wheel dimer, whereas polymer 2 exhibits a very weak antiferromagnetic interaction through the bpba linkers and/or space.

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Section: Description Of the Crystal Structuressupporting

confidence: 83%

Anion-Dependent Cu(II) Coordination Polymers: Geometric, Magnetic and Luminescent Properties

et al. 2022

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“…First, transesterification can lead to either intra- or intermolecular results by way of a lower M n or broader polydispersity index (PDI), respectively. Inefficient initiation of the catalytic system, which is the second reason, can result in several polymer chains growing faster than expected due to a much higher rate of initiation compared to the propagation step . However, variations of M n values with increasing conversion can be seen as polymerization proceeds (Figure ).…”

Section: Resultsmentioning

confidence: 98%

“…Inefficient initiation of the catalytic system, which is the second reason, can result in several polymer chains growing faster than expected due to a much higher rate of initiation compared to the propagation step. 60 However, variations of M n values with increasing conversion can be seen as polymerization proceeds ( Figure 7 ). For instance, the value of M n was 1.43 × 10 3 g mol –1 for 30 s, 2.06 × 10 3 g mol –1 for 1 min, 2.57 × 10 3 g mol –1 for 2 min, 3.18 × 10 3 g mol –1 for 5 min, and 3.59 × 10 3 g mol –1 for 10 min polymerization time.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of Zinc(II), Cadmium(II), and Palladium(II) Complexes with the Thiophene-Derived Schiff Base Ligand

et al. 2023

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Zn(II), Pd(II), and Cd(II) complexes, [L TH MCl 2 ] (M = Zn, Pd; X = Br, Cl) and [L TH Cd(μ-X)X] n (X = Cl, Br; n = n, 2), supported by the (E)-N 1,N 1-dimethyl-N 2-(thiophen-2-ylmethylene)ethane-1,2-diamine (L TH ) ligand are synthesized and structurally characterized. Density functional theory (DFT) electronic structure calculations and variable-temperature NMR support the presence of two conformers and a dynamic interconversion process of the minor conformer to the major one in solution. It is found that the existence of two relevant complex conformers and their respective ratios in solution depend on the central metal ions and counter ions, either Cl– or Br–. Among the two relevant conformers, a single conformer is crystallized and X-ray diffraction analysis revealed a distorted tetrahedral geometry for Zn(II) complexes, and a distorted square planar and square pyramidal geometry for Pd(II) and Cd(II) complexes, respectively. It is shown that [L TH MCl 2 ]/LiO i Pr (M = Zn, Pd) and [L TH Cd(μ-Cl)Cl] n /LiO i Pr can effectively catalyze the ring-opening polymerization (ROP) reaction of rac-lactide (rac-LA) with 94% conversion within 30 s with [L TH ZnCl 2 ]/LiO i Pr at 0 °C. Overall, hetero-enriched poly(lactic acid)s (PLAs) were provided by these catalytic systems with [L TH ZnCl 2 ]/LiO i Pr producing PLA with higher heterotactic bias (P r up to 0.74 at 0 °C).

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Effect of initiator on the catalytic performance of zinc(II) complexes supported by aminomethylquinoline and aminomethylpyridine derived ligands in stereoselective ring opening polymerization of rac-lactide

et al. 2022

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Ring opening polymerization of d,l-lactide and ε-caprolactone catalysed by (pyrazol-1-yl)copper(ii) carboxylate complexes

Abstract: We report the synthesis, structure and complete characterization of four new pyrazolyl carboxylate-based copper(ii) complexes that catalyze the ring opening polymerization of ε-caprolactone under solvent-free conditions and of d,l-lactide in toluene.

Cited by 6 publications

References 70 publications

Anion-Dependent Cu(II) Coordination Polymers: Geometric, Magnetic and Luminescent Properties

Anion-Dependent Cu(II) Coordination Polymers: Geometric, Magnetic and Luminescent Properties

Synthesis and Characterization of Zinc(II), Cadmium(II), and Palladium(II) Complexes with the Thiophene-Derived Schiff Base Ligand

Effect of initiator on the catalytic performance of zinc(II) complexes supported by aminomethylquinoline and aminomethylpyridine derived ligands in stereoselective ring opening polymerization of rac-lactide

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