Dinuclear Metal Complex-Mediated Formation of CO2-Based Polycarbonates

Romain, Charles; Thevenon, Arnaud; Saini, Prabhjot; Williams, Charlotte K.

doi:10.1007/3418_2015_95

Cited by 28 publications

(31 citation statements)

References 174 publications

(259 reference statements)

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“…[34][35][36] The viability of CO2/epoxide ROCOP depends on the selection of the metal catalyst which in turn controls rates, polymer molar mass and polymer composition (selectivity). [37][38][39][40] Amongst the highest performing catalysts are dinuclear, dimeric or bicomponent metal complexes. 35,[41][42][43][44][45][46][47] For highly active dinuclear catalyst, it is commonly proposed that one metal activates the epoxide while the other provides the attacking nucleophile.…”

Section: Introductionmentioning

confidence: 99%

Groups 1, 2 and Zn(II) Heterodinuclear Catalysts for Epoxide/CO₂ Ring-Opening Copolymerization

et al. 2018

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A series of heterodinuclear complexes are reported where both Zn(II) and a metal from Group 1 or 2 are chelated by a macrocyclic diphenolate-tetra-amine ligand. The complexes are characterized in the solid state, where relevant by single crystal X-ray crystallography and elemental analysis, and in solution, using NMR spectroscopy and mass spectrometry. The complex 2 synthesis is achieved by reaction of the ligand with diethyl zinc, to form the mono-zinc complex, in situ, followed by subsequent coordination of the second metal; this method enables heterodinuclear conversions >90 % as determined by NMR spectroscopy. Alternatively, the same heterodinuclear complexes are accessed by reaction between the two homodinuclear complexes, at elevated temperatures for extended periods. These findings suggest that most of the heterodinuclear complexes are the thermodynamic products; the only exception is the Na(I)/Zn(II) complex which is unstable with respect to the homodinuclear counterparts. The catalytic activities and selectivity of the stable heterodinuclear complexes are compared, against each other and the relevant homodinuclear analogues, for the ring opening copolymerization (ROCOP) of CO2 and CHO. Nearly all the heterodinuclear complexes are less active than the di-zinc analogues, but the Mg(II)/Zn(II) catalyst is more active. The co-ligand influences the product selectivity, with iodide ligands resulting in cyclic carbonate formation and carboxylate ligands in a high selectivity for polycarbonate.

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Section: Introductionmentioning

confidence: 99%

Groups 1, 2 and Zn(II) Heterodinuclear Catalysts for Epoxide/CO₂ Ring-Opening Copolymerization

et al. 2018

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“…However, it remains important to pursue CO 2 utilization as a means to reduce emissions, particularly those associated with existing, large-scale industrial processes and as an economic driver to support carbon capture [6,7]. The ROCOP process is strongly dependent on the selection of the catalyst, with various homogeneous and heterogeneous catalysts having been reported [5,[8][9][10][11][12][13][14][15]. The focus for this review article will be to highlight and exemplify some of the key findings in this area 2016 The Authors.…”

Section: Introductionmentioning

confidence: 99%

“…of catalysis, in particular using examples drawn from our own research. The intention is not to provide a comprehensive review of all known catalysts; indeed, such reviews are already available [5,[8][9][10][11][12][13][14][15]. The ROCOP reaction is a rare example of a truly catalytic process with the potential to deliver large-scale quantities of product, which genuinely consumes carbon dioxide.…”

Section: Introductionmentioning

confidence: 99%

Catalysts for CO ₂ /epoxide ring-opening copolymerization

Trott¹,

Saini²,

Williams³

2016

Phil. Trans. R. Soc. A.

185

142

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This article summarizes and reviews recent progress in the development of catalysts for the ring-opening copolymerization of carbon dioxide and epoxides. The copolymerization is an interesting method to add value to carbon dioxide, including from waste sources, and to reduce pollution associated with commodity polymer manufacture. The selection of the catalyst is of critical importance to control the composition, properties and applications of the resultant polymers. This review highlights and exemplifies some key recent findings and hypotheses, in particular using examples drawn from our own research.

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“…Metal synergy is often summoned as the rationale for the high performances and activities of bimetallic catalysts but detailed mechanistic insight and support for the putative cooperative interactions are far less frequently presented. 18,19 For example, synergic interactions are invoked in mechanisms underpinning large-scale processes such as polymerization, ammonia synthesis, methanol synthesis and Fischer-Tropsch reactions as well as for organic transformations from C-H activations to redox processes but so far detailed understanding of how to design catalysts to exploit or optimize synergy is lacking. [20][21][22][23] In the field of CO2/epoxide copolymerization, we have previously reported a series of dinuclear Zn(II)/Mg(II) catalysts and proposed their superior performances arose from synergic interactions (Fig.…”

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Understanding metal synergy in heterodinuclear catalysts for the copolymerization of CO2 and epoxides

et al. 2020

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The copolymerization of carbon dioxide with epoxides is an industrially relevant means to valorize wastes and improve sustainability in polymer manufacturing, and may also provide an economic benefit to CO2 capture and storage technologies. The efficiency of the process depends upon the catalyst used; previously Zn(II)Mg(II) heterodinuclear catalysts showed good performances at low CO2 pressures, which has been attributed to synergic interactions between the metals. Here we report a Mg(II)Co(II) catalyst for the production of polyols by copolymerization of CO2 with cyclohexene oxide that exhibits significantly better activity (turn-over-frequency over 12,000 h-1), high CO2 utilization (over 99 %) and high polymer selectivity (over 99 %). Detailed kinetic investigations show a second-order rate law, independent of CO2 pressure from 1 to 40 bar. Investigations of the synergy between the metal centres showed that epoxide coordination occurs at Mg(II) with reduced transition state entropy, which the carbonate attack step is accelerated at Co(II) through lowering of the transition state enthalpy. functionalization of alternating polyesters: selective patterning of (AB)n sequences.

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Dinuclear Metal Complex-Mediated Formation of CO2-Based Polycarbonates

Cited by 28 publications

References 174 publications

Groups 1, 2 and Zn(II) Heterodinuclear Catalysts for Epoxide/CO₂ Ring-Opening Copolymerization

Groups 1, 2 and Zn(II) Heterodinuclear Catalysts for Epoxide/CO₂ Ring-Opening Copolymerization

Catalysts for CO ₂ /epoxide ring-opening copolymerization

Understanding metal synergy in heterodinuclear catalysts for the copolymerization of CO2 and epoxides

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Dinuclear Metal Complex-Mediated Formation of CO2-Based Polycarbonates

Cited by 28 publications

References 174 publications

Groups 1, 2 and Zn(II) Heterodinuclear Catalysts for Epoxide/CO2 Ring-Opening Copolymerization

Groups 1, 2 and Zn(II) Heterodinuclear Catalysts for Epoxide/CO2 Ring-Opening Copolymerization

Catalysts for CO 2 /epoxide ring-opening copolymerization

Understanding metal synergy in heterodinuclear catalysts for the copolymerization of CO2 and epoxides

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Groups 1, 2 and Zn(II) Heterodinuclear Catalysts for Epoxide/CO₂ Ring-Opening Copolymerization

Groups 1, 2 and Zn(II) Heterodinuclear Catalysts for Epoxide/CO₂ Ring-Opening Copolymerization

Catalysts for CO ₂ /epoxide ring-opening copolymerization