A One‐Component Iron Catalyst for Cyclic Propylene Carbonate Synthesis

Dengler, Joachim; Lehenmeier, Maximilian W.; Klaus, Stephan; Anderson, Carly E.; Herdtweck, Eberhardt; Rieger, Bernhard

doi:10.1002/ejic.201000861

Cited by 100 publications

(50 citation statements)

References 79 publications

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“…[18] Iron(II)-Schiff base complexes have also been investigated as catalysts for propylene carbonate synthesis by Rieger and co-workers. [19] This work reports the successful conversion of the epoxide to the cyclic organic carbonate product without the use of an additional co-catalyst, although the conditions used were relatively harsh, namely 100 8C and 1.5 MPa of carbon dioxide pressure.…”

Section: Introductionmentioning

confidence: 98%

An Efficient Iron Catalyst for the Synthesis of Five‐ and Six‐Membered Organic Carbonates under Mild Conditions

et al. 2012

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An iron(III) amine triphenolate complex, [FeTPhOA]2, able to efficiently catalyze the cycloaddition of carbon dioxide to a range of terminal epoxides under mild conditions, is described. In addition, it has also been found that the complex is able to catalyze the conversion with more sterically congested oxiranes and oxetanes which are generally considered challenging substrates to activate. Variation of the co‐catalyst, required for ring‐opening of the substrates, has also been examined. The results show that terminal epoxide substrates are converted more efficiently with an iodide co‐catalyst, whereas more bulky oxirane substrates give better product yields in the presence of a bromide co‐catalyst. The combined results demonstrate the broad applicability of these iron(III) complexes in this type of carbon dioxide fixation chemistry.

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Section: Introductionmentioning

confidence: 98%

An Efficient Iron Catalyst for the Synthesis of Five‐ and Six‐Membered Organic Carbonates under Mild Conditions

et al. 2012

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“…[1][2][3][4] The methods to overcome the high kinetic barriers that are associated with the use of carbon dioxide for chemical synthesis are mainly based on reduction, oxidative coupling with unsaturated compounds on low valent transition-metal complexes or the nucleophilic attack on the carbonyl carbon. [3,5,6] With regard to industrial applications, the highest impact can be ascribed to the reactivity of CO 2 towards nucleophiles such as alkoxides, anionically opened epoxides and amines to give products such as salicylic acid (6 Mt CO 2 per year), cyclic carbonates (a few kt CO 2 per year; in this text, cyclic carbonate is used instead of more common designations such as propylene carbonate to distinguish the side product from polycarbonate) and urea (70 Mt CO 2 per year). [2,4] All of these nucleophiles are highly reactive molecules and can therefore be used to overcome the thermodynamic stability of carbon dioxide.…”

Section: Introductionmentioning

confidence: 98%

Differences in Reactivity of Epoxides in the Copolymerisation with Carbon Dioxide by Zinc‐Based Catalysts: Propylene Oxide versus Cyclohexene Oxide

Lehenmeier

Bruckmeier

Klaus

et al. 2011

Chemistry A European J

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The homogeneous dinuclear zinc catalyst going back to the work of Williams et al. is to date the most active catalyst for the copolymerisation of cyclohexene oxide and CO(2) at one atmosphere of carbon dioxide. However, this catalyst shows no copolymer formation in the copolymerisation reaction of propylene oxide and carbon dioxide, instead only cyclic carbonate is found. This behaviour is known for many zinc-based catalysts, although the reasons are still unidentified. Within our studies, we focus on the parameters that are responsible for this typical behaviour. A deactivation of the catalyst due to a reaction with propylene oxide turns out to be negligible. Furthermore, the catalyst still shows poly(cyclohexene carbonate) formation in the presence of cyclic propylene carbonate, but the catalyst activity is dramatically reduced. In terpolymerisation reactions of CO(2) with different ratios of cyclohexene oxide to propylene oxide, no incorporation of propylene oxide can be detected, which can only be explained by a very fast back-biting reaction. Kinetic investigations indicate a complex reaction network, which can be manifested by theoretical investigations. DFT calculations show that the ring strains of both epoxides are comparable and the kinetic barriers for the chain propagation even favour the poly(propylene carbonate) over the poly(cyclohexene carbonate) formation. Therefore, the crucial step in the copolymerisation of propylene oxide and carbon dioxide is the back-biting reaction in the case of the studied zinc catalyst. The depolymerisation is several orders of magnitude faster for poly(propylene carbonate) than for poly(cyclohexene carbonate).

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“…The main focus of numerous publications in this field was based on a dinuclear catalysts, which accommodate the epoxide ring opening and a CO 2 insertion in a single molecule. [8,10,12,[14][15][16][17][18][19][20][21] Zinc as a catalytically active species has tremendous advantages compared to other transition metals. It is an economic, ecofriendly element, and its ions are colorless.…”

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Flexibly Tethered Dinuclear Zinc Complexes: A Solution to the Entropy Problem in CO₂/Epoxide Copolymerization Catalysis?

et al. 2013

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A One‐Component Iron Catalyst for Cyclic Propylene Carbonate Synthesis

Cited by 100 publications

References 79 publications

An Efficient Iron Catalyst for the Synthesis of Five‐ and Six‐Membered Organic Carbonates under Mild Conditions

An Efficient Iron Catalyst for the Synthesis of Five‐ and Six‐Membered Organic Carbonates under Mild Conditions

Differences in Reactivity of Epoxides in the Copolymerisation with Carbon Dioxide by Zinc‐Based Catalysts: Propylene Oxide versus Cyclohexene Oxide

Flexibly Tethered Dinuclear Zinc Complexes: A Solution to the Entropy Problem in CO₂/Epoxide Copolymerization Catalysis?

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A One‐Component Iron Catalyst for Cyclic Propylene Carbonate Synthesis

Cited by 100 publications

References 79 publications

An Efficient Iron Catalyst for the Synthesis of Five‐ and Six‐Membered Organic Carbonates under Mild Conditions

An Efficient Iron Catalyst for the Synthesis of Five‐ and Six‐Membered Organic Carbonates under Mild Conditions

Differences in Reactivity of Epoxides in the Copolymerisation with Carbon Dioxide by Zinc‐Based Catalysts: Propylene Oxide versus Cyclohexene Oxide

Flexibly Tethered Dinuclear Zinc Complexes: A Solution to the Entropy Problem in CO2/Epoxide Copolymerization Catalysis?

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Flexibly Tethered Dinuclear Zinc Complexes: A Solution to the Entropy Problem in CO₂/Epoxide Copolymerization Catalysis?