Alternating copolymerization of carbon dioxide and epoxide by manganese porphyrin: The first example of polycarbonate synthesis from 1‐atm carbon dioxide

Sugimoto, H.; Ohshima, Hideki; Inoue, Shohei

doi:10.1002/pola.10835

Cited by 108 publications

(74 citation statements)

References 43 publications

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“…3 h À1 ). [6] Mechanistically, the independence of CHO conversion on the CO 2 pressure indicates that the insertion of CO 2 into the Zn À alkoxide bond is not the rate-determining step of the reaction.…”

Section: Resultsmentioning

confidence: 99%

“…[1] One of the most promising ways to effectively utilize CO 2 , the synthesis of polycarbonates through metal-catalyzed coupling reactions of CO 2 and epoxides, was first reported by Inoue et al in 1969 [2] and has attracted much attention over the past few decades. [3,4] A wide variety of catalytic systems, including both heterogeneous catalyst mixtures [5] and homogeneous discrete metal complex catalysts, [6][7][8][9][10][11][12][13][14] have been developed over the past decade with the latter being the focus of most current research owing not only to their high activities, but also to their well-defined structures that allow mechanistic investigations.…”

Section: Introductionmentioning

confidence: 99%

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Copolymerization of Cyclohexene Oxide with CO₂ by Using Intramolecular Dinuclear Zinc Catalysts

Xiao¹,

Wang²,

Ding³

2005

Chemistry A European J

220

141

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The intramolecular dinuclear zinc complexes generated in situ from the reaction of multidentate semi-azacrown ether ligands with Et(2)Zn, followed by treatment with an alcohol additive, were found to promote the copolymerization of CO(2) and cyclohexene oxide (CHO) with completely alternating polycarbonate selectivity and high efficiency. With this type of novel initiator, the copolymerization could be accomplished under mild conditions at 1 atm pressure of CO(2), which represents a significant advantage over most catalytic systems developed for this reaction so far. The copolymerization reaction was demonstrated to be a living process as a result of the narrow polydispersities and the linear increase in the molecular weight with conversion of CHO. In addition, the solid-state structure of the dinuclear zinc complex was characterized by X-ray crystal structural analysis and can be considered as a model of the active catalyst. On the basis of the various efforts made to understand the mechanisms of the catalytic reaction, including MALDI-TOF mass analysis of the copolymers' end-groups, the effect of alcohol additives on the catalysis and CO(2) pressure on the conversion of CHO, as well as the kinetic data gained from in situ IR spectroscopy, a plausible catalytic cycle for the present reaction system is outlined. The copolymerization is initiated by the insertion of CO(2) into the Zn--OEt bond to afford a carbonate-ester-bridged complex. The dinuclear zinc structure of the catalyst remains intact throughout the copolymerization. The bridged zinc centers may have a synergistic effect on the copolymerization reaction; one zinc center could activate the epoxide through its coordination and the second zinc atom may be responsible for carbonate propagation by nucleophilic attack by the carbonate ester on the back side of the cis-epoxide ring to afford the carbonate. The mechanistic implication of this is particularly important for future research into the design of efficient and practical catalysts for the copolymerization of epoxides with CO(2.).

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Copolymerization of Cyclohexene Oxide with CO₂ by Using Intramolecular Dinuclear Zinc Catalysts

Xiao¹,

Wang²,

Ding³

2005

Chemistry A European J

220

141

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“…Very recently, the first example of the alternating copolymerization (under 1 atm pressure) of carbon dioxide was achieved by Sugimoto et al 66 by employing a manganese porphyrin (10e) as the catalyst.…”

Section: Copolymerization By Manganese Complexesmentioning

confidence: 99%

Copolymerization of carbon dioxide and epoxide

Sugimoto

Inoue

2004

J. Polym. Sci. A Polym. Chem.

Self Cite

360

142

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An erratum has been published for this article in J Polym Sci Part A: Polym Chem (2005) 43(4) 916.The alternating copolymerization of carbon dioxide and epoxide to produce polycarbonate has attracted the attention of many chemists because it is one of the most promising methodologies for the utilization of carbon dioxide as a safe, clean, and abundant raw material in synthetic chemistry. Recent development of catalysts for alternating copolymerization is based on the rational design of metal complexes, particularly complexes of transition metals with well‐defined structures. In this article, the history and recent successful examples of the alternating copolymerization of carbon dioxide and epoxide are described. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5561–5573, 2004

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“…2). These include porphyrins and the closely related corroles [55,59,[68][69][70][71][72][73][74]; Schiff base ligands, most commonly salens/salans [40,46,75]; β-diiminates [76][77][78][79][80][81][82]; and (macrocyclic) phenoxy- amine ligands, including deliberately dinucleating macrocycles [63,65,[83][84][85][86][87][88]. The first two classes are dianionic and are largely targeted towards M(III) oxidation states, whereas the latter two are often used to prepare M(II) catalysts.…”

Section: Catalyst Classes and Scope Of The Reviewmentioning

confidence: 99%

Dinuclear Metal Complex-Mediated Formation of CO2-Based Polycarbonates

Romain

Thevenon

Saini

et al. 2015

Topics in Organometallic Chemistry

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This review describes selected metal catalysts for the copolymerisation of epoxides and carbon dioxide to produce polycarbonates. It highlights kinetic and mechanistic studies which have implicated di-or (multi-) metallic pathways for this catalysis and the subsequent development of highly active and selective di-/(multi-) nuclear catalysts. The emphasis is on homogeneous di-/bimetallic catalysts.

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Alternating copolymerization of carbon dioxide and epoxide by manganese porphyrin: The first example of polycarbonate synthesis from 1‐atm carbon dioxide

Cited by 108 publications

References 43 publications

Copolymerization of Cyclohexene Oxide with CO₂ by Using Intramolecular Dinuclear Zinc Catalysts

Copolymerization of Cyclohexene Oxide with CO₂ by Using Intramolecular Dinuclear Zinc Catalysts

Copolymerization of carbon dioxide and epoxide

Dinuclear Metal Complex-Mediated Formation of CO2-Based Polycarbonates

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Alternating copolymerization of carbon dioxide and epoxide by manganese porphyrin: The first example of polycarbonate synthesis from 1‐atm carbon dioxide

Cited by 108 publications

References 43 publications

Copolymerization of Cyclohexene Oxide with CO2 by Using Intramolecular Dinuclear Zinc Catalysts

Copolymerization of Cyclohexene Oxide with CO2 by Using Intramolecular Dinuclear Zinc Catalysts

Copolymerization of carbon dioxide and epoxide

Dinuclear Metal Complex-Mediated Formation of CO2-Based Polycarbonates

Contact Info

Product

Resources

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Copolymerization of Cyclohexene Oxide with CO₂ by Using Intramolecular Dinuclear Zinc Catalysts

Copolymerization of Cyclohexene Oxide with CO₂ by Using Intramolecular Dinuclear Zinc Catalysts