Catalytic Reactions Involving C<sub>1</sub> Feedstocks:  New High-Activity Zn(II)-Based Catalysts for the Alternating Copolymerization of Carbon Dioxide and Epoxides

Cheng, Ming; Lobkovsky, Emil; Coates, Geoffrey W.

doi:10.1021/ja982601k

Cited by 493 publications

(353 citation statements)

References 15 publications

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“…In this respect, the contributions from Coates and co-workers 21,22 described very active zinc b-diiminate catalysts for the synthesis of monodispersed, highly alternating carbon dioxide/epoxide copolymers with high molecular weight. In addition, the group of Williams 23 demonstrated a zinc-based macrocyclic bimetallic catalyst for epoxide/CO 2 copolymerization, which shows remarkable activity at only 1 bar of CO 2 .…”

Section: Box 1 | Coordination Modes Of Co 2 With Transition Metalsmentioning

confidence: 99%

Using carbon dioxide as a building block in organic synthesis

et al. 2015

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Carbon dioxide exits in the atmosphere and is produced by the combustion of fossil fuels, the fermentation of sugars and the respiration of all living organisms. An active goal in organic synthesis is to take this carbon-trapped in a waste product-and re-use it to build useful chemicals. Recent advances in organometallic chemistry and catalysis provide effective means for the chemical transformation of CO 2 and its incorporation into synthetic organic molecules under mild conditions. Such a use of carbon dioxide as a renewable one-carbon (C1) building block in organic synthesis could contribute to a more sustainable use of resources.A more sensible resource management is the prerequisite for the sustainable development of future generations. However, when dealing with the feedstock of the chemical industry, the level of sustainability is still far from satisfactory. Until now, the vast majority of carbon resources are based on crude oil, natural gas and coal. In addition to biomass, CO 2 offers the possibility to create a renewable carbon economy. Since pre-industrial times, the amount of CO 2 has steadily increased and nowadays CO 2 is a component of greenhouse gases, which are primarily responsible for the rise in atmospheric temperature and probably abnormal changes in the global climate. This increase in CO 2 concentration is largely due to the combustion of fossil fuels, which are required to meet the world's energy demand 1 . Obviously, there is an urgent need to control CO 2 emissions and develop efficient carbon capture systems. Although the extensive use of carbon dioxide for chemical production cannot solve this problem alone, CO 2 is a useful one-carbon (C1) building block in organic synthesis due to its abundance, availability, nontoxicity and recyclability. As a result, valorization of CO 2 is currently receiving considerable and ever increasing attention by the scientific community 2-4 . However, activation and utilization of CO 2 is still problematic due to the fact that it is the most oxidized form of carbon, which is also thermodynamically stable and/or kinetically inert in certain desired transformations. Consequently, most of the known studies used highly reactive substrates and/or severe reaction conditions to activate CO 2 , limiting the application of such methods. In particular, the catalytic coupling of CO 2 with energy-rich substrates, such as epoxides and aziridines, to generate polycarbonates/polycarbamates and/or cyclic carbonates/carbamates has drawn significant attention over the past decades. To create C-C bonds with CO 2 , the use of carbon nucleophiles is specifically limited to strong nucleophilic organolithiums and Grignard reagents, as well as phenolates.

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Section: Box 1 | Coordination Modes Of Co 2 With Transition Metalsmentioning

confidence: 99%

Using carbon dioxide as a building block in organic synthesis

et al. 2015

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“…Coates and his coworkers [23][24][25][26][27] have reported that zinc bis(␤-diiminates) (4) are more active than Darensbourg's zinc bis(phenoxides) (1) for the alternating copolymerization of carbon dioxide and cyclohexene oxide. The zinc bis(␤-diiminates) (4) were dimeric in the solid state, as shown by X-ray crystallographic analysis, 23 whereas the 1 H NMR data showed that 4 was monomeric in solution.…”

Section: Copolymerization By Zinc ␤-Diiminatesmentioning

confidence: 99%

“…The zinc bis(␤-diiminates) (4) were dimeric in the solid state, as shown by X-ray crystallographic analysis, 23 whereas the 1 H NMR data showed that 4 was monomeric in solution.…”

Section: Copolymerization By Zinc ␤-Diiminatesmentioning

confidence: 99%

Copolymerization of carbon dioxide and epoxide

Sugimoto

Inoue

2004

J. Polym. Sci. A Polym. Chem.

364

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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“…Recently, several efficient catalyst systems for the copolymerization of CO 2 and alicyclic epoxides such as cyclohexene oxide have been reported to offer significant advantages over traditional heterogeneous catalysts. [6][7][8][9][10][11][12] Unfortunately, these catalysts do not readily polymerize CO 2 and aliphatic epoxides such as propylene oxide (PO). Recently, Coates and co-workers [13] reported the first highly active zinc b-diiminate catalysts bearing electron-withdrawing groups for the synthesis of poly(propylene carbonate) (PPC) with carbonate linkages up to 99 %, but along with the formation of cyclic propylene carbonate (PC; 7-25 %).…”

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Highly Active, Binary Catalyst Systems for the Alternating Copolymerization of CO₂ and Epoxides under Mild Conditions

2004

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Chemical fixation of CO 2 is of great interest with respect to the development of truly environmentally benign processes, as there are many possibilities for CO 2 to be used as a safe and cheap C 1 feedstock in organic synthesis. [1] One of the most promising reactions in this area is the alternating copolymerization of CO 2 and epoxides to polycarbonates, [2] which was first reported by Inoue et al. [3] These polycarbonates not only exhibit interesting material properties, but also have the additional environmental advantages resulting from their biodegradability. [4] In recent decades, numerous catalyst systems have been developed for this transformation. [5] Although the advances have been significant, high catalyst loading, elevated CO 2 pressure, and long reaction time are usually prerequisites for obtaining appreciable amounts of polymer, which are often not perfectly alternating and exhibit broad molecular-weight distributions. Recently, several efficient catalyst systems for the copolymerization of CO 2 and alicyclic epoxides such as cyclohexene oxide have been reported to offer significant advantages over traditional heterogeneous catalysts. [6][7][8][9][10][11][12] Unfortunately, these catalysts do not readily polymerize CO 2 and aliphatic epoxides such as propylene oxide (PO). Recently, Coates and co-workers [13] reported the first highly active zinc b-diiminate catalysts bearing electron-withdrawing groups for the synthesis of poly(propylene carbonate) (PPC) with carbonate linkages up to 99 %, but along with the formation of cyclic propylene carbonate (PC; 7-25 %). A simple decrease in temperature and increase in CO 2 pressure suppressed the formation of PC and increased the selectivity for PPC. A similar effect was reported by Darensbourg and co-workers, who used chiral salen chromium chloride, alone or in conjunction with Nmethylimidazole as a catalyst, for this reaction. [14] Herein, we report the use of a highly active binary catalyst system, which consists of a chiral cobalt complex [(salcy)Co iii X] and a quaternary ammonium salt (nBu 4 NY) for completely alternating copolymerization of CO 2 and aliphatic epoxides under extremely mild conditions. Pursuant to our own efforts toward the development of highly efficient catalysts for coupling CO 2 with epoxides under mild conditions, [15] we became interested in the possibility of developing catalyst systems for the direct synthesis of optically active cyclic carbonates from racemic epoxides, which are inexpensive or easily accessible from inexpensive commercial starting materials. Based on the fact that chiral [(salcy)Co iii ] complexes (Jacobsen catalyst) were shown to be highly efficient and enantioselective catalysts for the hydrolytic kinetic resolution of terminal epoxides, [16] we recently designed a bifunctional nucleophile-electrophile catalyst system consisting of chiral [(salcy)Co iii ] complexes and quaternary ammonium salts for the direct synthesis of optically active cyclic carbonates from racemic epoxides. [17] In this system, the ...

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Catalytic Reactions Involving C₁ Feedstocks: New High-Activity Zn(II)-Based Catalysts for the Alternating Copolymerization of Carbon Dioxide and Epoxides

Cited by 493 publications

References 15 publications

Using carbon dioxide as a building block in organic synthesis

Using carbon dioxide as a building block in organic synthesis

Copolymerization of carbon dioxide and epoxide

Highly Active, Binary Catalyst Systems for the Alternating Copolymerization of CO₂ and Epoxides under Mild Conditions

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Catalytic Reactions Involving C1 Feedstocks: New High-Activity Zn(II)-Based Catalysts for the Alternating Copolymerization of Carbon Dioxide and Epoxides

Cited by 493 publications

References 15 publications

Using carbon dioxide as a building block in organic synthesis

Using carbon dioxide as a building block in organic synthesis

Copolymerization of carbon dioxide and epoxide

Highly Active, Binary Catalyst Systems for the Alternating Copolymerization of CO2 and Epoxides under Mild Conditions

Contact Info

Product

Resources

About

Catalytic Reactions Involving C₁ Feedstocks: New High-Activity Zn(II)-Based Catalysts for the Alternating Copolymerization of Carbon Dioxide and Epoxides

Highly Active, Binary Catalyst Systems for the Alternating Copolymerization of CO₂ and Epoxides under Mild Conditions