Cyclic organic carbonates represent a relevant class of chemicals that can be prepared from CO2 by cycloaddition to epoxides. The application of efficient catalysts is crucial in allowing the cycloaddition reaction to proceed under very mild conditions of temperature, pressure, and CO2 concentration, thus resulting in a sustainable and carbon-balanced approach to CO2 conversion. This is particularly the case if impure waste CO2 could be employed as a feedstock. In this Review, we have critically analyzed the burgeoning literature on the cycloaddition of CO2 to epoxides with the aim to provide state-of-the-art knowledge on the catalysts that can convert CO2 to carbonates under ambient conditions. These have been systematically organized in families of compounds and critically scrutinized in terms of catalytic activity, availability and mechanistic features. Finally, we provide an overview on the catalytic systems able to function using diluted and impure CO2 as a feedstock.

Catalytic Strategies for the Cycloaddition of Pure, Diluted, and Waste CO2 to Epoxides under Ambient Conditions

https://pubs.rsc.org/en/content/articlepdf/2019/gc/c8gc03086c

CO2-fixation into cyclic and polymeric carbonates: Principles and applications

Carbon dioxide offers an accessible, cheap and renewable carbon feedstock for synthesis. Current interest in the area of carbon dioxide valorisation aims at new, emerging technologies that are able to provide new opportunities to turn a waste into value. Polymers are among the most widely produced chemicals in the world greatly affecting the quality of life. However, there are growing concerns about the lack of reuse of the majority of the consumer plastics and their after-life disposal resulting in an increasing demand for sustainable alternatives. New monomers and polymers that can address these issues are therefore warranted, and merging polymer synthesis with the recycling of carbon dioxide offers a tangible route to transition towards a circular economy. Here, an overview of the most relevant and recent approaches to CO2-based monomers and polymers are highlighted with particular emphasis on the transformation routes used and their involved manifolds.

Advances in the use of CO2 as a renewable feedstock for the synthesis of polymers

The combination of a chromium(III) salophen bromide complex and tetrabutylammonium bromide is shown to catalyze the reaction between terminal epoxides and carbon dioxide at ambient temperature and 1 bar carbon dioxide pressure and between internal epoxides and carbon dioxide at 80 °C and 10 bar carbon dioxide pressure to form cyclic carbonates. The optimal conditions involve the use of 1.5–2.5 mol % of both the chromium(III) salophen bromide complex and tetrabutylammonium bromide and result in the formation of cyclic carbonates in 57–92% isolated yields after a reaction time of 24 h. Under these conditions, no polycarbonate formation is observed except when cyclohexene oxide is used as substrate. The reactions were found to proceed with retention of epoxide stereochemistry. A study of the reaction kinetics revealed that the chromium(III) complex and tetrabutylammonium bromide react together to form a six-coordinate anionic chromium complex which is the actual catalyst, and a catalytic cycle is proposed wh...

Cr(salophen) Complex Catalyzed Cyclic Carbonate Synthesis at Ambient Temperature And Pressure

The use of CO2 as a C1 building block will be of essential importance in the future. In this context the synthesis of cyclic carbonates from epoxides and CO2 gained great attention recently. These products are valuable compounds in a variety of chemical fields. The development of new catalysts and catalytic systems for this atom-economic, scalable, and industrially relevant reaction is a highly active research field. Over the past 17 years great advances have been made in this area of research. This chapter covers the survey of the important known classes of homogeneous catalysts for the addition of CO2 to epoxides. Besides pioneering work, recent developments and procedures that allow this transformation under mild reaction conditions (reaction temperatures of ≤100 °C and/or CO2 pressures of 0.1 MPa) are especially emphasized.

Recent Developments in the Synthesis of Cyclic Carbonates from Epoxides and CO 2

Readily available ascorbic acid was discovered as an environmentally benign hydrogen bond donor for the synthesis of cyclic organic carbonates from CO2 and epoxides in the presence of nucleophilic cocatalysts. The ascorbic acid/TBAI (TBAI: tetrabutylammonium iodide) binary system could be applied for the cycloaddition of CO2 to various epoxides under ambient or mild conditions. Density functional theory calculations and catalysis experiments revealed an intriguing bifunctional mechanism in the step of CO2 insertion involving different hydroxyl moieties (enediol, ethyldiol) of the ascorbic acid scaffold.

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Ascorbic Acid as a Bifunctional Hydrogen Bond Donor for the Synthesis of Cyclic Carbonates from CO2 under Ambient Conditions

Highly integrated CO2 capture and conversion: direct synthesis of cyclic carbonates from industrial flue gas

A reusable zirconium-based catalyst for the cycloaddition of CO 2 to propylene oxide (PO) was prepared by the surface organometallic chemistry (SOMC) methodology. Accordingly, well-defined amounts of the ZrCl 4 ·(OEt 2 ) 2 precursor were grafted on the surface of silica dehydroxylated at 700 °C (SiO 2-700 ) and at 200 °C (SiO 2-200 ) in order to afford surface coordination compounds with different podality and chemical environment. The identity of the surface complexes was thoroughly investigated by FT-IR, elemental microanalysis and solid state NMR and applied as a recoverable and reusable heterogeneous catalyst for the title reaction using pure CO 2 and flue gas samples from a cement factory. The observed catalytic activity for the isolated zirconium complexes is rationalized by means of systematic DFT calculations.

Alexander Barthel

Papers

Ascorbic Acid as a Bifunctional Hydrogen Bond Donor for the Synthesis of Cyclic Carbonates from CO2 under Ambient Conditions

Highly integrated CO2 capture and conversion: direct synthesis of cyclic carbonates from industrial flue gas

Conversion of actual flue gas CO2 via cycloaddition to propylene oxide catalyzed by a single-site, recyclable zirconium catalyst