Synthesis of Methanol and Diols from CO<sub>2</sub> via Cyclic Carbonates under Metal-Free, Ambient Pressure, and Solvent-Free Conditions

Bobbink, Félix D.; Menoud, Florent; Dyson, Paul J.

doi:10.1021/acssuschemeng.8b02453

Cited by 35 publications

(15 citation statements)

References 49 publications

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“…Moreover, the ease of recording high-quality 29 Si NMR spectra suggests tremendous promise akin to tagging a reagent with 19 F . Casual survey of the literature suggests that, despite the prevalence of silyl groups and silyl-based protecting groups, 29 Si NMR spectroscopy is being underutilized . It would be a superb tool to monitor reactions and products by the organic synthesis community.…”

Section: Discussionmentioning

confidence: 99%

Aggregation and Solvation of Sodium Hexamethyldisilazide: Across the Solvent Spectrum

Woltornist

Collum

2021

J. Org. Chem.

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We report solution structures of sodium hexamethyldisilazide (NaHMDS) solvated by >30 standard solvents (ligands). These include: toluene, benzene, and styrene; triethylamine and related trialkylamines; pyrrolidine as a representative dialkylamine; dialkylethers including THF, tert-butylmethyl ether, and diethyl ether; dipolar ligands such as DMF, HMPA, DMSO, and DMPU; a bifunctional dipolar ligand nonamethylimidodiphosphoramide (NIPA); polyamines N,N,N′,N′-tetramethylenediamine (TMEDA), N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDTA), N,N,N′,N′-tetramethylcyclohexanediamine (TMCDA), and 2,2′-bipyridine; polyethers 12-crown-4, 15-crown-5, 18-crown-6, and diglyme; 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane ([2.2.2] cryptand); and tris[2-(2-methoxyethoxy)ethyl]amine (TDA-1). Combinations of 1H, 13C, 15N, and 29Si NMR spectroscopies, the method of continuous variations, X-ray crystallography, and density functional theory (DFT) computations reveal ligand-modulated aggregation to give mixtures of dimers, monomers, triple ions, and ion pairs. 15N–29Si coupling constants distinguish dimers and monomers. Solvation numbers are determined by a combination of solvent titrations, observed free and bound solvent in the slow exchange limit, and DFT computations. The relative abilities of solvents to compete in binary mixtures often match that predicted by conventional wisdom but with some exceptions and evidence of both competitive and cooperative (mixed) solvation. Crystal structures of a NaHMDS cryptate ion pair and a 15-crown-5-solvated monomer are included. Results are compared with those for lithium hexamethyldisilazide, lithium diisopropylamide, and sodium diisopropylamide.

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Section: Discussionmentioning

confidence: 99%

Aggregation and Solvation of Sodium Hexamethyldisilazide: Across the Solvent Spectrum

Woltornist

Collum

2021

J. Org. Chem.

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“…It could be expected that epoxide and carbonate might be competing for the Mn axial vacancy site, but not the diol. Since no diol production is observed in initial stages of the reaction, it is assumed that its formation is a result of carbonate degradation . Thus, selectivity may be affected in longer reactions and higher temperatures due to degradation of carbonate to form diol.…”

Section: Resultsmentioning

confidence: 99%

“…Since no diol production is observed in initial stages of the reaction, it is assumed that its formation is a result of carbonate degradation. [21] Thus, selectivity may be affected in longer reactions and higher temperatures due to degradation of carbonate to form diol. On the other hand, in temperatures below 70°C, even in presence of water, selectivity is high showing the robustness of our system in mild conditions.…”

Section: Catalytic Studies On the Cycloaddition Reactionmentioning

confidence: 99%

Mn^III Porphyrins: Catalytic Coupling of Epoxides with CO₂ under Mild Conditions and Mechanistic Considerations

et al. 2019

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A series of 5,10,15,20‐tetrakis(2,3‐dichlorophenyl)porphyrinate complexes of manganese(III) [MnIII(T2,3DCPP)X] with six different axial ligands (X=NO3−, AcO−, IO3−, Br−, Cl−, HO−) were investigated as catalysts in the cycloaddition reactions of CO2 and styrene oxide (SO), under mild conditions, i. e., atmospheric pressure and 60 °C. [MnIIIT(2,3DCPP)IO3] showed the best catalytic performance, selectively producing the respective cyclic carbonate from diverse epoxides using tetrabutylammonium bromide as a nucleophile source. Mechanistic considerations were inferred from electronic spectra and spectrophotometric titrations, showing that there are a series of equilibriums involved in the formation of the catalytic active species. Stability constants for the proposed equilibrium models were determined using SQUAD software. A catalytic cycle has been proposed based on those observations.

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“…[15] With this notion in mind, we combined our research on the cycloaddition of CO 2 with epoxides to produce cyclic carbonates, with other research on hydrogenation reactions, which resulted in a simple approach for the production of methanol and diols from CO 2 and epoxides (Figure 2). [16,17] This pathway may be considered as an extension of the OMEGA process (production of monoethylene glycol through the hydrolysis of ethylene carbonate obtained from CO 2 -ethylene oxide coupling). In the first step, i. e., the CO 2 -epoxide coupling reaction, we employed a simple IL catalyst to transform an epoxide selectively into its corresponding cyclic carbonate.…”

Section: The Original Research: Indirect Co 2 Methanationmentioning

confidence: 99%

A Semi‐Serendipitous Journey towards the Commercialisation of a Catalytic Hydrocracking Process for Polymer Waste

Bobbink¹,

Muyden²,

Lee

et al. 2022

ChemPlusChem

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This Personal Account reviews the sequence of scientific discoveries that led to a catalytic plastic conversion technology that resulted in the creation of a spin-off company called Plastogaz from the Ecole Polytechnique Fédérale de Lausanne (Switzerland). The story begins with research on the catalytic valorization of CO 2 , carried out by two PhD students and a master student, and the connections and steps subsequently made, ultimately leading to a plastic transformation technology. The Personal Account highlights the value of diverse research topics within a research group, the benefits of connections between chemistry and chemical engineering, that can lead to interesting synergies and atypical breakthroughs.

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Synthesis of Methanol and Diols from CO₂ via Cyclic Carbonates under Metal-Free, Ambient Pressure, and Solvent-Free Conditions

Cited by 35 publications

References 49 publications

Aggregation and Solvation of Sodium Hexamethyldisilazide: Across the Solvent Spectrum

Aggregation and Solvation of Sodium Hexamethyldisilazide: Across the Solvent Spectrum

Mn^III Porphyrins: Catalytic Coupling of Epoxides with CO₂ under Mild Conditions and Mechanistic Considerations

A Semi‐Serendipitous Journey towards the Commercialisation of a Catalytic Hydrocracking Process for Polymer Waste

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Synthesis of Methanol and Diols from CO2 via Cyclic Carbonates under Metal-Free, Ambient Pressure, and Solvent-Free Conditions

Cited by 35 publications

References 49 publications

Aggregation and Solvation of Sodium Hexamethyldisilazide: Across the Solvent Spectrum

Aggregation and Solvation of Sodium Hexamethyldisilazide: Across the Solvent Spectrum

MnIII Porphyrins: Catalytic Coupling of Epoxides with CO2 under Mild Conditions and Mechanistic Considerations

A Semi‐Serendipitous Journey towards the Commercialisation of a Catalytic Hydrocracking Process for Polymer Waste

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Product

Resources

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Synthesis of Methanol and Diols from CO₂ via Cyclic Carbonates under Metal-Free, Ambient Pressure, and Solvent-Free Conditions

Mn^III Porphyrins: Catalytic Coupling of Epoxides with CO₂ under Mild Conditions and Mechanistic Considerations