Dinuclear zinc catalysts with unprecedented activities for the copolymerization of cyclohexene oxide and CO<sub>2</sub>

Kissling, Stefan; Lehenmeier, Maximilian W.; Altenbuchner, Peter T.; Kronast, Alexander; Reiter, Marina; Deglmann, Peter; Seemann, Uwe B.; Rieger, Bernhard

doi:10.1039/c5cc00784d

Cited by 141 publications

(111 citation statements)

References 34 publications

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“…[35][36][37][38] The group of Williams demonstrated a zinc-based macrocyclic bimetallic catalyst, which showed remarkable activity even at atmospheric pressure of carbon dioxide. [39][40][41] More recently, Rieger et al [42][43][44] reported dinuclear zinc-b-diiminate complexes and Dinjus and co-workers Notably, most of these systems require halogen containing compounds, such as ammonium and phosphonium salts which are commonly employed co-catalyst for the synthesis of cyclicas well as polycarbonates from epoxides and CO 2 . We are generally interested in the reaction between epoxides and CO 2 .…”

Section: -23mentioning

confidence: 99%

Copolymerization of CO₂ and epoxides mediated by zinc organyls

2018

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Herein we report the copolymerization of CHO with CO 2 in the presence of various zinc compounds R 2 Zn (R ¼ Et, Bu, iPr, Cy and Ph). Several zinc organyls proved to be efficient catalysts for this reaction in the absence of water and co-catalyst. Notably, readily available Bu 2 Zn reached a TON up to 269 and an initial TOF up to 91 h À1 . The effect of various parameters on the reaction outcome has been investigated. Poly(ether)carbonates with molecular weights up to 79.3 kg mol À1 and a CO 2 content of up to 97% were obtained. Under standard reaction conditions (100 C, 2.0 MPa, 16 h) the influence of commonly employed co-catalysts such as PPNCl and TBAB has been investigated in the presence of Et 2 Zn (0.5 mol%). The reaction of other epoxides (e.g. propylene and styrene oxide) under these conditions led to no significant conversion or to the formation of the respective cyclic carbonate as the main product.

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Section: -23mentioning

confidence: 99%

Copolymerization of CO₂ and epoxides mediated by zinc organyls

2018

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“…While some catalysts for CO 2 /epoxide copolymerization are active even at the most desirable pressure of 1 atm CO 2 , they usually suffer from a number of different limitations . These include low chemoselectivity for the target polycarbonate, especially at low pressures; the use of toxic metals and additives; low turnover number (TON) and turnover frequency (TOF) values, and low catalyst isolation yields .…”

Section: Methodsmentioning

confidence: 99%

“…obtained for similar polymerization conditions . Furthermore, 1 differs from the so far known catalysts in that no additional coligands (such as acetate, HMDS, or solvents) are present in the employed complex . In this case, an external nucleophile (e.g., water) or the zinc‐bound (non‐bridging) alkoxido groups may initiate the polymerization.…”

Section: Methodsmentioning

confidence: 99%

Highly Active and Readily Accessible Proline‐Based Dizinc Catalyst for CO₂/Epoxide Copolymerization

Schütze

Dechert

Meyer

2017

Chemistry A European J

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In the pursuit of CO -based materials, the development of efficient catalysts for the alternating copolymerization of CO and epoxides to give polycarbonates is receiving particular attention. Desirable attributes for such catalysts are high copolymerization activity at low CO pressure, as well as chemo- and stereocontrol over the formed polymer. Here, we report a novel chiral zinc catalyst that can be isolated in 97 % yield from commercial sources, and that produces polycarbonates selectively from neat cyclohexene oxide under 1 bar of CO pressure at temperatures above 50 °C. At 80 °C reaction temperature, TONs of 1684 and initial TOFs up to 149 h were measured, producing an isotactic-enriched polycarbonate with a probability P of 65 % for the formation of a meso diad. Insight into the dinuclear nature of the active species and the copolymerization progress has been gained from structural and spectroscopic studies.

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“…Apart from them, other types of macrocyclic bis(β‐diimine)s have been reported, which originate from the condensation of primary diamines with viii ) bis(β‐aminocarbonyl) and bis(β‐aminothiocarbonyl) compounds, respectively, or ix ) the ethylene glycol monoketal of β‐diones . Alternatively, macrocyclic compounds are also formed in the reaction of metallated bis(imine)s and bis(imidoylchloride)s (route x , Scheme ) …”

Section: Bis(β‐diimine)smentioning

confidence: 99%

Ligands with Two Monoanionic N,N‐Binding Sites: Synthesis and Coordination Chemistry

Kretschmer

2019

Chemistry A European J

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Polytopic ligands have become ubiquitous in coordination chemistry because they grant access to a variety of mono‐ and polynuclear complexes of transition metals as well as rare‐earth and main‐group elements. Nitrogen‐based ditopic ligands, in which two monoanionic N,N‐binding sites are framed within one molecule, are of particular importance and are therefore the primary focus of this review. In detail, bis(amidine)s, bis(guanidine)s, bis(β‐diimine)s, bis(aminotroponimine)s, bis(pyrrolimine)s, and miscellaneous bis(N,N‐chelating) ligands are reviewed. In addition to the general synthetic protocols, the application of these ligands is discussed along with their coordination chemistry, the multifarious binding modes, and the ability of these ligands to bridge two (or more) metal(loids).

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Dinuclear zinc catalysts with unprecedented activities for the copolymerization of cyclohexene oxide and CO₂

Cited by 141 publications

References 34 publications

Copolymerization of CO₂ and epoxides mediated by zinc organyls

Copolymerization of CO₂ and epoxides mediated by zinc organyls

Highly Active and Readily Accessible Proline‐Based Dizinc Catalyst for CO₂/Epoxide Copolymerization

Ligands with Two Monoanionic N,N‐Binding Sites: Synthesis and Coordination Chemistry

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Dinuclear zinc catalysts with unprecedented activities for the copolymerization of cyclohexene oxide and CO2

Cited by 141 publications

References 34 publications

Copolymerization of CO2 and epoxides mediated by zinc organyls

Copolymerization of CO2 and epoxides mediated by zinc organyls

Highly Active and Readily Accessible Proline‐Based Dizinc Catalyst for CO2/Epoxide Copolymerization

Ligands with Two Monoanionic N,N‐Binding Sites: Synthesis and Coordination Chemistry

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Dinuclear zinc catalysts with unprecedented activities for the copolymerization of cyclohexene oxide and CO₂

Copolymerization of CO₂ and epoxides mediated by zinc organyls

Copolymerization of CO₂ and epoxides mediated by zinc organyls

Highly Active and Readily Accessible Proline‐Based Dizinc Catalyst for CO₂/Epoxide Copolymerization