Mechanistic Investigation and Reaction Kinetics of the Low-Pressure Copolymerization of Cyclohexene Oxide and Carbon Dioxide Catalyzed by a Dizinc Complex

The reaction kinetics of the copolymerization of carbon dioxide and cyclohexene oxide to produce poly(cyclohexene carbonate), catalyzed by a dizinc acetate complex, is studied by in situ attenuated total reflectance infrared (ATR-IR) and proton nuclear magnetic resonance (¹H NMR) spectroscopy. A parameter study, including reactant and catalyst concentration and carbon dioxide pressure, reveals zero reaction order in carbon dioxide concentration, for pressures between 1 and 40 bar and temperatures up to 80 °C, and a first-order dependence on catalyst concentration and concentration of cyclohexene oxide. The activation energies for the formation of poly(cyclohexene carbonate) and the cyclic side product cyclohexene carbonate are calculated, by determining the rate coefficients over a temperature range between 65 and 90 °C and using Arrhenius plots, to be 96.8 ± 1.6 kJ mol^–1 (23.1 kcal mol^–1) and 137.5 ± 6.4 kJ mol^–1 (32.9 kcal mol^–1), respectively. Gel permeation chromatography (GPC), ¹H NMR spectroscopy, and matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) mass spectrometry are employed to study the poly(cyclohexene carbonate) produced, and reveal bimodal molecular weight distributions, with narrow polydispersity indices (≤1.2). In all cases, two molecular weight distributions are observed, the higher value being approximately double the molecular weight of the lower value; this finding is seemingly independent of copolymerization conversion or reaction parameters. The copolymer characterization data and additional experiments in which chain transfer agents are added to copolymerization experiments indicate that rapid chain transfer reactions occur and allow an explanation for the observed bimodal molecular weight distributions. The spectroscopic and kinetic analyses enable a mechanism to be proposed for both the copolymerization reaction and possible side reactions; a dinuclear copolymerization active site is implicated

Experimental and Computational Investigation of the Mechanism of Carbon Dioxide/Cyclohexene Oxide Copolymerization Using a Dizinc Catalyst

A detailed study of the mechanism by which a dizinc catalyst copolymerizes cyclohexene oxide and carbon dioxide is presented. The catalyst, previously published by Williams et al. (Angew. Chem. Int. Ed. 2009, 48, 931), shows high activity under just 1 bar pressure of CO₂. This work applies <i>in situ</i> attenuated total reflectance infrared spectroscopy (ATR-FTIR) to study changes to the catalyst structure on reaction with cyclohexene oxide and, subsequently, with carbon dioxide. A computational investigation, using DFT with solvation corrections, is used to calculate the relative free energies for various transition states and intermediates in the cycle for alternating copolymerization catalyzed by this dinuclear complex. Two potentially competing side reactions, sequential epoxide enchainment and sequential carbon dioxide enchainment are also investigated. The two side-reactions are shown to be thermodynamically disfavored, rationalizing the high selectivity exhibited in experimental studies using <b>1</b>. Furthermore, the DFT calculations show that the rate-determining step is the nucleophilic attack of the coordinated epoxide molecule by the zinc-bound carbonate group in line with previous experimental findings (ΔΔ<i>G</i>₃₅₃ = 23.5 kcal/mol; Δ<i>G</i>^‡₃₅₃ = 25.7 kcal/mol). Both <i>in situ</i> spectroscopy and DFT calculations indicate that just one polymer chain is initiated per dizinc catalyst molecule. The catalyst adopts a “bowl” shape conformation, whereby the acetate group coordinated on the concave face is a spectator ligand while that coordinated on the convex face is the initiating group. The spectator carboxylate group plays an important role in the catalytic cycle, counter-balancing chain growth on the opposite face. The DFT was used to predict the activities of two new catalysts, good agreement between experimental turn-over-numbers and DFT predictions were observed

Experimental and Computational Investigation of the Mechanism of Carbon Dioxide/Cyclohexene Oxide Copolymerization Using a Dizinc Catalyst

A detailed study of the mechanism by which a dizinc catalyst copolymerizes cyclohexene oxide and carbon dioxide is presented. The catalyst, previously published by Williams et al. (Angew. Chem. Int. Ed. 2009, 48, 931), shows high activity under just 1 bar pressure of CO₂. This work applies <i>in situ</i> attenuated total reflectance infrared spectroscopy (ATR-FTIR) to study changes to the catalyst structure on reaction with cyclohexene oxide and, subsequently, with carbon dioxide. A computational investigation, using DFT with solvation corrections, is used to calculate the relative free energies for various transition states and intermediates in the cycle for alternating copolymerization catalyzed by this dinuclear complex. Two potentially competing side reactions, sequential epoxide enchainment and sequential carbon dioxide enchainment are also investigated. The two side-reactions are shown to be thermodynamically disfavored, rationalizing the high selectivity exhibited in experimental studies using <b>1</b>. Furthermore, the DFT calculations show that the rate-determining step is the nucleophilic attack of the coordinated epoxide molecule by the zinc-bound carbonate group in line with previous experimental findings (ΔΔ<i>G</i>₃₅₃ = 23.5 kcal/mol; Δ<i>G</i>^‡₃₅₃ = 25.7 kcal/mol). Both <i>in situ</i> spectroscopy and DFT calculations indicate that just one polymer chain is initiated per dizinc catalyst molecule. The catalyst adopts a “bowl” shape conformation, whereby the acetate group coordinated on the concave face is a spectator ligand while that coordinated on the convex face is the initiating group. The spectator carboxylate group plays an important role in the catalytic cycle, counter-balancing chain growth on the opposite face. The DFT was used to predict the activities of two new catalysts, good agreement between experimental turn-over-numbers and DFT predictions were observed

Experimental and Computational Investigation of the Mechanism of Carbon Dioxide/Cyclohexene Oxide Copolymerization Using a Dizinc Catalyst

A detailed study of the mechanism by which a dizinc catalyst copolymerizes cyclohexene oxide and carbon dioxide is presented. The catalyst, previously published by Williams et al. (Angew. Chem. Int. Ed. 2009, 48, 931), shows high activity under just 1 bar pressure of CO₂. This work applies <i>in situ</i> attenuated total reflectance infrared spectroscopy (ATR-FTIR) to study changes to the catalyst structure on reaction with cyclohexene oxide and, subsequently, with carbon dioxide. A computational investigation, using DFT with solvation corrections, is used to calculate the relative free energies for various transition states and intermediates in the cycle for alternating copolymerization catalyzed by this dinuclear complex. Two potentially competing side reactions, sequential epoxide enchainment and sequential carbon dioxide enchainment are also investigated. The two side-reactions are shown to be thermodynamically disfavored, rationalizing the high selectivity exhibited in experimental studies using <b>1</b>. Furthermore, the DFT calculations show that the rate-determining step is the nucleophilic attack of the coordinated epoxide molecule by the zinc-bound carbonate group in line with previous experimental findings (ΔΔ<i>G</i>₃₅₃ = 23.5 kcal/mol; Δ<i>G</i>^‡₃₅₃ = 25.7 kcal/mol). Both <i>in situ</i> spectroscopy and DFT calculations indicate that just one polymer chain is initiated per dizinc catalyst molecule. The catalyst adopts a “bowl” shape conformation, whereby the acetate group coordinated on the concave face is a spectator ligand while that coordinated on the convex face is the initiating group. The spectator carboxylate group plays an important role in the catalytic cycle, counter-balancing chain growth on the opposite face. The DFT was used to predict the activities of two new catalysts, good agreement between experimental turn-over-numbers and DFT predictions were observed